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Hydrolysis of the vinylidene complex [Ru(η5-C5H5){=C=C(H)Ph} (PPh3){P(OMe)3}]BPh4 afforded the mixed-ligands carbonyl derivative [Ru(η5-C5H5)(CO)(PPh3){P(OMe)3}]BPh4. Its structure has been determined by X-ray diffraction. The compound crystallizes in the monoclinic crystal system, space group P21/c, with one anion and one cation in the asymmetric unit. The cation complex contains a ruthenium atom in a half-sandwich piano-stool structure. One trimethylphosphito, one triphenylphosphine and one carbonyl ligand are the legs of the stool.

Chloro complexes IrCl2(η5-C5Me5)[P(OR)3] (1) (R Me, Et) were prepared by reacting dimer [IrCl2(η5-C5Me5)]2 with phosphites in alcohol. Treatment of 1 with R1NHNH2 gave monohydrazine complexes [IrCl(η5-C5Me5)(R1NHNH2){P(OR)3}]BPh4 (2, 3, 4) [R1 H (2), Me (3), Ph (4)]. Bis(hydrazine) complexes [Ir(η5-C5Me5)(R1NHNH2)2{P(OR)3}](BPh4)2 (5, 6) were prepared by reacting chloro complexes first with AgOTf and then with an excess of hydrazine. Oxidation with Pb(OAc)4 at −40 °C of both mono- and bis(hydrazine) complexes afforded phenyldiazene derivatives [IrCl(η5-C5Me5)(PhN NH){P(OR)3}]BPh4 (7) and [Ir(η5-C5Me5)(PhN NH)2{P(OR)3}](BPh4)2 (9). Bis(aryldiazene) [Ir(η5-C5Me5)(PhN NH)2{P(OR)3}](BPh4)2 (9, 10) were also prepared by allowing hydride IrH2(η5-C5Me5)[P(OR)3] (8) to react with aryldiazonium cations [ArN2]BF4. The complexes were characterised spectroscopically and by X-ray crystal structure determination of [IrCl(η5-C5Me5)(NH2NH2){P(OEt)3}]BPh4 (2b) and [IrCl(η5-C5Me5)(CH3NHNH2){P(OEt)3}]BPh4 (3b).

Polypyridyl complexes [RuCl(η5-C5Me5)(N–N)] (1–4) [N–N 2,2′-bipyridine (bpy) (1), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bpy) (2), 1,10-phenanthroline (phen) (3) and 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen) (4)] were prepared by reacting [RuCl2(η5-C5Me5)]2 with Zn dust in the presence of polypyridyl ligands. Unlike the related [RuCl(η5-C5Me5)(L1)(L2)]+ [L1, L2 = P(OR)3, PPh3] derivatives with P-donor ligands, treatment of chloro compounds 1–4 with diazoalkanes Ar1Ar2CN2 afforded polypyridyl carbene complexes [Ru(η5-C5Me5)( CAr1Ar2)(N–N)]BPh4 (5–8) [Ar1 = Ar2 = Ph (a), Ar1 = Ph, Ar2 = p-tolyl (b)]. Comparative DFT studies of the formation of metallacarbenes from aromatic diazoalkanes are reported. Phosphite complex [Ru(η5-C5Me5)(bpy){P(OEt)3}]BPh4 (9) and acetylide derivatives [Ru(η5-C5Me5)(C CAr)(bpy)] (10, 11) [Ar = Ph (10), p-tolyl (11)] were also obtained by substitution of the carbene in 5–8. Unstable vinylidene cations [Ru(η5-C5Me5){ C C(H)Ar](bpy)]+ (12, 13) were formed by protonation with HBF4•Et2O of acetylide species 10, 11. The complexes were characterized spectroscopically (IR and 1H, 13C, 31P NMR) and by X-ray crystal structure determination of [Ru(η5-C5Me5){ C(Ph)(p-tolyl)}(bpy)]BPh4 (5b).

Unlike what was previously reported, the reaction of the hydrazine derivative [Ru(NH2NH2)2{P(OEt)3}4](BPh4)2 with p-tolyldiazonium tetrafluoroborate in CH2Cl2 afforded the boranehydrazine complex [RuCl(κ1-NH2NH2BPh3){P(OEt)3}4]BPh4. The complex was characterised spectroscopically (IR and NMR) and by X-ray crystal structure determination.

Hydrazine complexes [Ru(η5-C5Me5)(NH2NHR1){P(OR)3}L]BPh4 (1–4) [R1 = H, Me, Ph; L = P(OR)3, PPh3; R = Me, Et] were prepared by the reaction of chloro compounds [RuCl(η5-C5Me5){P(OR)3}L] with hydrazines in the presence of NaBPh4. When exposed to air in CH2Cl2 solution, the phenylhydrazine derivatives 1c–4c afforded the sandwich complex [Ru(η5-C5Me5)(η6-C6H6)]BPh4 (5). A reaction path involving the formation of a phenyldiazene complex as an intermediate compound is discussed. The oxidation of hydrazine complexes 1–4 with Pb(OAc)4 at −40 °C yielded diazene derivatives [Ru(η5-C5Me5)(NHNR1){P(OR)3}L]BPh4 (6–9) [R1 = Me, Ph; L = P(OR)3, PPh3]. Aryldiazene complexes [Ru(η5-C5Me5)(NHNAr){P(OR)3}L]BPh4 (7, 9) (Ar = Ph, p-tolyl) were also prepared by allowing hydride [RuH(η5-C5Me5){P(OR)3}L] (10, 11) to react with aryldiazonium salts ArN2+BF4− in CH2Cl2. The complexes were characterised by spectroscopy (IR, 1H, 31P, and 15N NMR) and the X-ray crystal structure of [Ru(η5-C5Me5)(NH2NH2){P(OEt)3}2]BPh4 (2a) and [Ru(η5-C5Me5)(η6-C6H6)]BPh4 (5) was determined.

Diazoalkane complexes [Os(η5-C5Me5)(N2CAr1Ar2)(PPh3){P(OR)3}]BPh4 (1, 2) [R = Me (1), Et (2); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (fluorenyl) (c)] were prepared by reacting bromo-compounds OsBr(η5-C5Me5)(PPh3){P(OR)3} with an excess of diazoalkane in ethanol. The treatment of diazoalkane complexes 1 and 2 with acetylene under mild conditions (1 atm, RT) led to dipolar (3 + 2) cycloaddition affording 3H-pyrazole derivatives [Os(η5-C5Me5)(η1-[upper bond 1 start]N[double bond, length as m-dash]NC(C12H8)CH[double bond, length as m-dash]C[upper bond 1 end]H)(PPh3){P(OR)3}]BPh4 (6, 7) [R = Me (6), Et (7)] whereas reactions with terminal alkynes R1C[triple bond, length as m-dash]CH (R1 = Ph, p-tolyl, COOMe) gave vinylidene derivatives [Os(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)R1}(PPh3){P(OR)3}]BPh4 (8b-d, 9b-d) [R = Me (8), Et (9); R1 = Ph (b), p-tolyl (c), COOMe (d)]. Exposure to air of dichloromethane solutions of complexes 1 and 2 produced dioxygen derivatives [Os(η5-C5Me5)(η2-O2)(PPh3){P(OR)3}]BPh4 (10, 11) [R = Me (10), Et (11)]. Allenylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C[double bond, length as m-dash]CR1R2 (12-14) [R1 = R2 = Ph (12, 13); R1 = Ph, R2 = Me (14)], vinylvinylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C(H)C(Ph)[double bond, length as m-dash]CH2 (15) and 3-hydroxyvinylidene [Os][double bond, length as m-dash]C[double bond, length as m-dash]C(H)C(H)R2(OH) (16, 17) [R2 = Ph (16), H (17)] derivatives were also prepared. The vinylidene complex [Os(η5-C5Me5)([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PPh3){P(OMe)3}]BPh4 (8a) reacted with PPh3 to afford the alkenylphosphonium derivative [Os(η5-C5Me5){η1-C(H)[double bond, length as m-dash]C(H)PPh3}(PPh3){P(OMe)3}]BPh4 (18) whereas vinylidene complexes 8 and 9 reacted with water leading to the hydrolysis of the alkyne and the formation of carbonyl complexes [Os(η5-C5Me5)(CO)(PPh3){P(OR)3}]BPh4 (19, 20). The complexes were characterised by spectroscopic data (IR and NMR) and by X-ray crystal structure determination of [Os(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)p-tolyl}(PPh3){P(OEt)3}]BPh4 (9c), [Os(η5-C5Me5)(η2-O2)(PPh3){P(OMe)3}]BPh4 (10) and [Os(η5-C5Me5)(CO)(PPh3){P(OMe)3}]BPh4 (19).

The diazoalkane complexes [Ru(η(5)-C5Me5)(N2CAr1Ar2){P(OR)3}L]BPh4 (1-4) [R = Me, L = P(OMe)3 (1); R = Et, L = P(OEt)3 (2); R = Me, L = PPh3 (3); R = Et, L = PPh3 (4); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c); Ar1 = Ph, Ar2 = PhC(O) (d)] and [Ru(η(5)-C5Me5){N2C(C12H8)}{PPh(OEt)2}(PPh3)]BPh4 (5c) were prepared by allowing chloro-compounds RuCl(η(5)-C5Me5)[P(OR)3]L to react with the diazoalkane Ar1Ar2CN2 in the presence of NaBPh4. Treatment of complexes 1-4 with H2O afforded 1,2-diazene derivatives [Ru(η(5)-C5Me5)(η(2)-NH═NH){P(OR)3}L]BPh4 (6-9) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack by H2O on the coordinated diazoalkane is proposed and supported by density functional theory calculations. The complexes were characterized spectroscopically (IR and (1)H, (31)P, (13)C, (15)N NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5Me5)(N2CC12H8){P(OEt)3}2]BPh4 (2c) and [Ru(η(5)-C5Me5)(η(2)-NH═NH){P(OEt)3}2]BPh4 (7).

Ethylene complexes [OsH(η2-CH2=CH2)L4]Y (1, 2) [L = PPh(OEt)2, P(OEt)3; Y = OTf, BPh4] were prepared by reacting the dihydride OsH2L4 first with methyl triflate CH3OTf and then with ethylene (1 atm). Alternatively, the compound [OsH(η2-CH2=CH2){PPh(OEt)2}4]OTf was prepared by allowing the dinitrogen derivative [OsH(N2){PPh(OEt)2}4]OTf to react with ethylene. Acrylonitrile CH2=C(H)CN reacts with OsH(OTf)L4 [L = P(OEt)3] to give the complex [OsH{κ1-NCC(H)=CH2}{P(OEt)3}4]BPh4 (3). The complexes were characterized spectroscopically (IR and 1H, 13C, 31P NMR) and by X-ray crystal structure determination of the [OsH(η2-CH2=CH2){PPh(OEt)2}4]BPh4 derivative.

Diazoalkane complexes [Fe(eta(5)-C5H5)(N(2)CAr1Ar2)(P-P)]BPh4 (1, 2) [P-P = Ph2PCH2CH2PPh2 (dppe) (1), Ph2PCH2CH2CH2PPh2 (dppp) (2); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c)] were prepared by allowing chloro compounds FeCl(eta(5)-C5H5)(P-P) to react with diazoalkane in the presence of NaBPh4. Phosphine complex [Fe(eta(5)-C5H5)(dppe)(kappa(1)-PPh2CH2CH2PPh2)]BPh4 (3) was also prepared. Treatment of diazoalkane complexes 1, 2 with acrylonitrile afforded 3H-pyrazole derivatives [Fe(eta(5)- C5H5)-{N=NC(Ar1Ar2)(CH(CN)CH2}(P-P)]BPh4 (4, 5), as well as a small amount of nitrile complex [Fe(eta(5)-C5H5)(kappa(1)-NCC(H)]= CH2)(P-P)]BPh4 (6). The complexes were characterised spectroscopically (IR, NMR) and by X-ray crystal structure determination of [Fe(eta(5)-C5H5){N2C(C12H8)}(dppe)]BPh4 (1c).

Organic azide complexes [Os(η5-C5H5)(κ1-N3R)(PPh3){P(OR1)3}]BPh4 (1, 2) [R = CH2C6H5 (a), CH2C6H4-4-CH3 (b), CH(CH3)C6H5 (c), C6H5 (d); R1 = Me (1), Et (2)] were prepared by allowing bromo-compounds [OsBr(η5-C5H5)(PPh3){P(OR1)3}] to react first with AgOTf and then with an excess of azide in toluene. Benzylazide complexes reacted in solution leading to imine derivatives [Os(η5-C5H5){κ1-NH[double bond, length as m-dash]C(R2)Ar}(PPh3){P(OR1)3}]BPh4 (3, 4) [R2 = H (a, b), CH3 (c); Ar = C6H5, C6H4-4-CH3; R1 = Me (3), Et (4)]. Phenylazide, on the other hand, reacted in solution affording the dinuclear dinitrogen complex [{Os(η5-C5H5)(PPh3)[P(OMe)3]}2(μ-N2)](BPh4)2 (5). Depending on the nature of the R substituent, the reaction of the p-cymene complex [OsCl2(η6-p-cymene)(PPh3){P(OEt)3}] with RN3 yielded imine [OsCl(η6-p-cymene){κ1-NH[double bond, length as m-dash]C(H)Ar}{P(OEt)3}]BPh4 (6) (Ar = C6H4-4-CH3) and amine derivatives [OsCl(η6-p-cymene)(κ1-NH2C6H5){P(OEt)3}]BPh4 (7). The complexes were characterised spectroscopically (IR, 1H, 31P, 15N NMR) and by the X-ray crystal structure determination of [{Os(η5-C5H5)(PPh3)[P(OMe)3]}2(μ-N2)](BPh4)2 (5).

Dioxygen complexes [Ru(η5-C5Me5)(η2-O2){P(OEt)3}2]BPh4 (1) and [Ru(η5-C5Me5)(η2-O2)(PPh3){P(OR)3}]BPh4 (2, 3) [R = Me (2), Et (3)] were prepared by allowing chloro-complexes RuCl(η5-C5Me5)[P(OEt)3]2 and RuCl(η5-C5Me5)(PPh3)[P(OR)3] to react with air (1 atm) in the presence of NaBPh4. Substitution of the η2-O2 in 1-3 by alkenes [CH2[double bond, length as m-dash]CH2, [upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O] and terminal alkynes (PhC[triple bond, length as m-dash]CH) afforded [Ru(η5-C5Me5)(η2-CH2[double bond, length as m-dash]CH2){P(OEt)3}L]BPh4 (4) [L = P(OEt)3 (a), PPh3 (b)], [Ru(η5-C5Me5){η2-[upper bond 1 start]CH[double bond, length as m-dash]CHCO(O)C[upper bond 1 end]O}{P(OEt)3}2]BPh4 (5) and [Ru(η5-C5Me5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)Ph}{P(OEt)3}2]BPh4 (6) derivatives. Protonation of dioxygen complexes 1-3 with triflic acid yielded phosphate complexes [Ru(κ1-OTf)(η5-C5Me5){P(O)(OEt)3}2] (7) and [Ru(κ1-OTf)(η5-C5Me5){P(O)Ph3}{P(O)(OMe)3}] (8). A reaction path for the formation of complexes 7 and 8 is proposed by DFT studies. Besides phosphate complex 7, protonation of 1 under a CH2[double bond, length as m-dash]CH2 atmosphere (1 atm) afforded acetic acid. Treatment of complexes 7 and 8 with tBuNC afforded the tris(isocyanide) derivative [Ru(η5-C5Me5)(tBuNC)3]BPh4 (9). The complexes were characterised spectroscopically (IR and NMR) and by X-ray crystal structure determination of 1, 2 and 3.

Trichlorostannyl complexes [Ru(SnCl3) (Cp')L] (2a-c) were prepared by treatment of optically active half-sandwich chlorocomplexes [RuCl(Cp')L] (1a-c) with an excess of SnCl2.2H2O in ethanol. Treatment of trichlorostannyl complexes 2a-c with NaBH4 afforded trihydridostannyl derivatives [Ru(SnH3) (Cp')L] (3a-c) in moderated yields. Treatment of 2a-c with MgBrMe gave the trimethylstannyl complexes Ru(SnMe3) (Cp')L (4a-c). Alkynylstannyl derivatives [Ru{Sn(C≡CPh)3}(Cp')L] (5a-c) were prepared by treatment of trichlorostannyl compounds 2a-c with an excess of LiC≡CPh in thf. All the complexes present optical activity. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuCl(η5-C5Me5)L] (1b), [Ru(SnCl3) (η5-C5Me5)L] (2b), and [Ru(SnCl3) (η5-C9H7)L] (2c). The influence of different ligands on the Ru P interaction in several complexes 1a-c, 2a-c and 3a-c was evaluated by DFT calculations. These calculations indicate that [SnCl3]- has a stronger stabilization effect than [Cl]- and the same occurs between C9H7 and C5Me5. These relative stabilities combined with the distortion energies of the fragments produce a stabilizing effect in the Ru P bonds of complex 2c that is twice as strong as in the 1b complex.

Treatment of bis(cyanamide) [M(N≡CNEt2)2L4](BPh4)2 and bis(cyanoguanidine) [M{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 complexes [M = Fe, Ru, Os; L = P(OEt)3] with an excess of amine RNH2 (R = nPr, iPr) affords mixed-ligand complexes with cyanamide and amine [M(NH2R)(N≡CNEt2)L4](BPh4)2 (1a–5a) and [M(NH2R){N≡CN(H)C(NH2)=NH}L4](BPh4)2 (1b, 2b). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [M(NH2iPr)(N≡CNEt2){P(OEt)3}4](BPh4)2 [M = Ru (3a), Os (5a)].

Diazoalkane complexes [Ru(η(5)-C9H7)(N2CAr1Ar2)(PPh3)L]BPh4 (1-3) [L = PPh3, P(OMe)3, P(OEt)3; Ar1 = Ar2 = Ph; Ar1 = Ph, Ar2 = p-tolyl; Ar1Ar2 = C12H8 fluorenyl] were prepared by allowing chloro-complexes [RuCl(η(5)-C9H7)(PPh3)L] to react with an excess of diazoalkane in ethanol. Complexes 1-3 reacted with ethylene CH2=CH2 (1 atm) and maleic anhydride [ma, CH=CHCO(O)CO] to afford η(2)-alkene complexes [Ru(η(5)-C9H7)(η(2)-CH2=CH2)(PPh3)L]BPh4 (4, 5) and [Ru(η(5)-C9H7){η(2)-CH=CHCO(O)CO}(PPh3)L]BPh4 (7). Further, complexes 1-3 underwent cycloaddition with acrylonitrile CH2=C(H)CN, giving 1H-pyrazoline derivatives [Ru(η(5)-C9H7){η(1)-N=C(CN)CH2C(Ar1Ar2)NH}(PPh3)L]BPh4 (6). Treatment of diazoalkane complexes 1-3 with acetylene CH[triple bond, length as m-dash]CH under mild conditions (1 atm, room temperature) led to dipolar cycloaddition, affording 3H-pyrazole complexes [Ru(η(5)-C9H7)-{η(1)-N=NC(Ar1Ar2)CH=CH}(PPh3)L]BPh4 (8), whereas reaction with terminal alkynes RC≡CH (R = Ph, p-tolyl, Bu(t)) gave vinylidene derivatives [Ru(η(5)-C9H7){=C=C(H)R}(PPh3)L]BPh4 (9). The latter reacted with nucleophiles such as amines and alcohols to give amino- and alkoxy-carbene derivatives [Ru(η(5)-C9H7){=C(NHPr(n))(CH2Ph)}(PPh3)L]BPh4 (11) and [Ru(η(5)-C9H7){=C(CH3)(OEt)}(PPh3)L]BPh4 (10), respectively. In addition, complexes 9 reacted with phenylhydrazine to afford nitrile derivatives [Ru(η(5)-C9H7)(N[triple bond, length as m-dash]CCH2R)(PPh3)L]BPh4 (12) and phenylamine, whereas the reaction with water led to hydrolysis of the alkyne and formation of carbonyl complexes [Ru(η(5)-C9H7)(CO)(PPh3)L]BPh4 (13). Lastly, treatment of vinylidene complexes with the phosphines PPh3 and P(OMe)3 afforded alkenylphosphonium derivatives [Ru(η(5)-C9H7){C(H)=C(R)PPh3}(PPh3)L]BPh4 (14) and [Ru(η(5)-C9H7){C(R)=C(H)P(OMe)3}(PPh3)L]BPh4 (15), respectively. Compound [Ru(η(5)-C9H7){C(H)=C(H)PPh3}(PPh3)L]BPh4 (16) was also prepared. The complexes were characterised by spectroscopy (IR and NMR) and X-ray crystal structure determinations of [Ru(η(5)-C9H7){N2C(C12H8)}(PPh3){P(OEt)3}]BPh4 (3c), [Ru(η(5)-C9H7){=C=C(H)Ph}(PPh3){P(OEt)3}]BPh4 (9d) and [Ru(η(5)-C9H7){C(H)=C(Ph)PPh3}(PPh3){P(OEt)3}]BPh4 (14d).

Arylaldazine and acetoneazine complexes [IrCl(η5-C5Me5){κ1-[NC(H)(R2C6H4)]–NC(H)(R2C6H4)}{P(OR1)3}]BPh4 (1, 2) and [IrCl(η5-C5Me5){κ1-[NC(CH3)2]–NC(CH3)2}{P(OR1)3}]BPh4 (3, 4) [R1 = Me (1, 3), Et (2, 4); R2 = H (a), 4-CH3 (b), 2,6-(CH3)2 (f)] were prepared by allowing chloro complexes IrCl2(η5-C5Me5)[P(OR1)3] to react first with AgOTf and then with the appropriate azine. In solution, κ1-complexes 1–4 undergo a metalation reaction, affording chelate κ2-azine derivatives [Ir{κ2-R2C6H3(H)CN–NC(H)(R2C6H4)}(η5-C5Me5){P(OR1)3}]BPh4 (5, 6) and [Ir{κ2-CH2(CH3)CN–NC(CH3)2}(η5-C5Me5){P(OR1)3}]BPh4 (7, 8) [R1 = Me (5, 7), Et (6, 8); R2 = H (a), 4-CH3 (b), 4-CH3O (c); 4-F (d), 4-NO2 (e)]. The complexes were characterised spectroscopically and by X-ray crystal structure determination of [Ir{κ2-C6H4(H)CN–NC(H)(C6H5)}(η5-C5Me5){P(OEt)3}]BPh4 (6a). Most of the κ2-arylazine derivatives showed photoluminescence properties upon excitation with near-UV and violet light, with emission peaks at around 650 nm. The photoluminescence features were rationalised according to DFT calculations.

Half-sandwich azine complexes [OsCl(η6-p-cymene){ κ 1-[N=C(H)C6H4R1]–N=C(H)C6H4R1}-{P(OR)3}]BPh4 (1, 2) and [OsCl(η 6-p-cymene){κ 1-[N=C(CH3)2]N=C(CH3)2}{P(OR)3}]BPh4 (3, 4) [R = Me (1, 3), Et (2, 4); R1 = H (a), 4-CH3 (b), 2,6-(CH3)2 (c)] were prepared by allowing chloro compounds [OsCl2(η 6-p-cymene){P(OR)3}] to react first with one equivalent of AgOTf and then with azine. Instead, treatment of chloro compounds with acetone azine afforded hydrazone derivatives [OsCl(η 6-p-cymene){NH2N=C(CH3)2}{P(OR)3}]BPh4 (5, 6) [R = Me (5), Et (6)]. In solution, κ 1-azine complexes undergo metalation reaction, giving chelate derivatives [Os{ κ 2-R1C6H3C(H)=N–N=C(H)C6H4R1}(η 6-p-cymene){P(OR)3}]BPh4 (7, 8) [R = Me (7), Et (8); R1 = H (a), 4-CH3 (b)]. The complexes were characterised by spectroscopy (IR, NMR) and X-ray crystal structure determination of [OsCl(η 6-p-cymene){ κ 1-[N=C(H)Ph]–N=C(H)Ph}{P(OEt)3}]-BPh4 (2a).

Hydrazine complexes [Ru(η5-C5H5)(RNHNH2)(PPh3){P(OMe)3}]BPh4 (1–3) and [Ru(η5-C9H7)(RNHNH2) (PPh3){P(OEt)3}]BPh4 (4–6) (R = H, Me, Ph) were prepared by allowing chloro-compounds RuCl(η5-C5H5) (PPh3)[P(OMe)3] and RuCl(η5-C9H7) (PPh3)[P(OEt)3] to react with an excess of hydrazine in refluxing ethanol. Treatment of complexes 1–6 with Pb(OAc)4 at −40 °C yielded diazene derivatives [Ru(η5-C5H5)(RN NH) (PPh3){P(OMe)3}]BPh4 (7, 8) and [Ru(η5-C9H7) (RN NH)(PPh3){P(OEt)3}]BPh4 (10, 11) (R = Me, Ph). Aryldiazene complexes [Ru(η5-C5H5)(RN NH)(PPh3){P(OMe)3}]BPh4 (8, 9) (R = Ph, p-tolyl) were also prepared by allowing hydride RuH(η5-C5H5)(PPh3)[P(OMe)3] to react with aryldiazonium salts [RN2]+BF4– in CH2Cl2. The complexes were characterised by spectroscopy (IR, 1H, 31P NMR) and X-ray crystal structure determination of [Ru(η5-C9H7)(PhNHNH2)(PPh3){P(OEt)3}]BPh4 (6).

Aminophosphonium salts [Ph3PN(H)R]BPh4 (1) [R = C6H5CH2 (1a), 4-CH3C6H4CH2 (1b), C6H5 (1c)] were obtained by allowing hydride IrHCl2(PPh3)2{P(OEt)3} to react first with triflic acid and then with the organic azide RN3. The compounds were characterized spectroscopically and by X-ray crystal structure determination of [Ph3PN(H)CH2C6H4-4-CH3]BPh4 (1b). A reaction path for the formation of aminophosphonium cations is also proposed.

Trichlorostannyl complexes Ru(SnCl3)(η5-C9H7)(PPh3)L (1; L = P(OMe)3, P(OEt)3) were prepared by allowing chloro compounds RuCl(η5-C9H7)(PPh3)L to react with SnCl2·2H2O in ethanol. Treatment of compounds 1 with NaBH4 in ethanol yielded the tin trihydride derivatives Ru(SnH3)(η5-C9H7)(PPh3)L (2). The reaction of trichlorostannyl complexes 1 with MgBrMe in diethyl ether afforded the chlorodimethylstannyl derivatives Ru(SnClMe2)(η5-C9H7)(PPh3)L (3), whereas reaction with Li+C≡CPh– in THF yielded the trialkynylstannyl compounds Ru[Sn(C≡CPh)3](η5-C9H7)(PPh3)L (4). Treatment of the trihydridostannyl complexes 2 with the alkyl propiolate HC≡CCOOR led to the trivinylstannyl derivatives Ru[Sn{C(COOR)═CH2}3](η5-C9H7)(PPh3)L (5, 6; R = Me, Et). However, the reaction of [Ru]–SnH3 (2) with the propargylic alcohol HC≡CCPh2OH yielded the alkene H2C═C(H)CPh2OH and the hydride RuH(η5-C9H7)(PPh3)L (7). Treatment of tin trihydride complexes 2 with H2O led to the trihydroxostannyl derivatives Ru[Sn(OH)3](η5-C9H7)(PPh3)L (8). ...

Diazoalkane complexes [Ru(η5-C5H5)(N2CAr1Ar2)(PPh3)L]BPh4 (1, 2; Ar1 = Ph, Ar2 = p-tolyl; Ar1Ar2 = C12H8; L = P(OMe)3, P(OEt)3) were prepared by allowing compounds RuCl(η5-C5H5)(PPh3)L to react with diazoalkane in ethanol. Treatment of complexes 1 and 2 with ethylene under mild conditions (1 atm, room temperature) led not only to the ethylene complexes [Ru(η5-C5H5)(η2-CH2═CH2)(PPh3)L]BPh4 (5, 6) but also to dipolar (3 + 2) cycloaddition, affording the 3H-pyrazole derivatives [Ru(η5-C5H5){η1-N═NC(Ar1Ar2)CH2CH2}(PPh3)L]BPh4 (3, 4). The propylene complexes [Ru(η5-C5H5)(η2-CH3CH═CH2)(PPh3)L]BPh4 (7, 8) were also prepared. The compounds were characterized by spectroscopy and by X-ray crystal structure determinations of 2a, 3b, and 7.

Coordination compounds with the formulae [Y(MAA)3]x (1Y), [Ln(MAA)3]x (1Ln), [Y(MAA)3(phen)] (2Y) and [Ln(MAA)3(phen)] (2Ln) (Ln = Sm, Eu, Tb, Dy, Yb; MAA = conjugate base of methyl 3-oxo-butanoate; phen = 1,10-phenantroline) were synthesized and characterized, and X-ray diffraction data were collected for [Tb(MAA)3(phen)] (2Tb) and [Yb(MAA)3(phen)] (2Yb). Most of the lanthanide derivatives showed appreciable luminescence in the solid state upon excitation with near-UV light. Strong emissions were observed in particular for complexes of lanthanide ions with high-energy resonance levels. Visible-emitting [Ln(MAA)3(phen)] compounds were successfully used as dopants for the preparation of luminescent poly(methylmethacrylate) samples. Similar derivatives of the conjugate base of dimethyl malonate (DMM), with formulae [Y(DMM)3(phen)] (3Y) and [Ln(DMM)3(phen)] (3Ln) (Ln = Eu, Tb, Dy), were also synthesized and their photoluminescence behaviour was compared to that of the analogous methyl 3-oxo-butanoato-complexes.

Aldazine complexes [RuCl(η6-p-cymene){κ1-[N=C(H)R1]-N=C(H)R1}L]BPh4 (1-4) [L=P(OMe)3, P(OEt)3, PPh(OEt)2, PiPr3; R1=Ph, 4-CH3C6H4, 4-CH3OC6H4, Et] were prepared by allowing chloro compounds RuCl2(η6-p-cymene)L to react with the azine R1(H)C=N-N=C(H)R1 in ethanol. Depending on the nature of the phosphine ligand, the reaction of ketazine (CH3)2C=N-N=C(CH3)2 with chloro compounds RuCl2(η6-p-cymene)L yielded either hydrazone derivatives [RuCl(η6-p-cymene){NH2N=C(CH3)2}L]BPh4 (5,6) [L=P(OMe)3, P(OEt)3] or κ1-azine complex [RuCl(η6-p-cymene){κ1-[N=C(CH3)2]N=C(CH3)2}(PiPr3)]BPh4 (7). Cyclopentadienyl derivatives [Ru(η5-C5H5){κ1-[N=C(H)R1]-N=C(H)R1}(PPh3){P(OMe)3}]+ (10) [R1=Ph, 4-CH3C6H4, C2H5] were prepared by reacting the chloro compound RuCl(η5-C5H5)(PPh3)[P(OMe)3] first with AgOTf and then with an excess of azine. Instead, treatment of RuCl(η5-C5H5)(PPh3)[P(OMe)3] first with AgOTf and then with ketazine (CH3)2C=N-N=C(CH3)2 in ethanol, yielded hydrazone derivative [Ru(η5-C5H5){NH2N=C(CH3)2}(PPh3){P(OMe)3}]BPh4 (11). Oxidation of hydrazone derivative 11 with HgO gave dimethyldiazoalkane complex [Ru(η5-C5H5){N2C(CH3)2}(PPh3){P(OMe)3}]BPh4 (13). The complexes were characterised by spectroscopy and X-ray crystal structure determination of [RuCl(η6-p-cymene){κ1-[N=C(H)Ph]-N=C(H)Ph}{P(OMe)3}]BPh4 (1 a), [RuCl(η6-p-cymene){κ1-[N=C(H)Ph]-N=C(H)Ph}{P(OEt)3}]BPh4 (2 a) and [Ru(η5-C5H5){NH2N=C(CH3)2}(PPh3){P(OMe)3}]BPh4 (11).

1,10-Phenanthroline-5,6-dione (Phd) complexes of group 3 and lanthanide elements having formulae Ln(hfac)3(Phd) (Ln = Y, Eu, Yb; hfac = hexafluoroacetylacetonate) were synthesised and characterised. Complexes of d-block elements of the type [MCl(Phd)(p-cymene)]+ (M = Ru, Os) were also prepared. In all these species, coordination of the polydentate ligand occurs by the N-donor moieties, as indicated by DFT calculations. The novel compounds were tested, together with fac-ReBr(Phd)(CO)3, as precursors for the preparation of heterobimetallic d/f derivatives. The reaction of the rhenium complex with yttrium or lanthanide anhydrous triflate salts led to the formation of the complexes ReBr(CO)3(N,N′-Phd-O,O′)Ln(OTf)3(THF) (Ln = Y, Eu, Yb), where the trivalent ions interacted with the quinonoid moiety. The redox properties of the rhenium centre were strongly affected by the coordination of Ln(OTf)3, as observed by comparing the cyclic voltammetry measurements carried out on fac-ReBr(Phd)(CO)3 and on ReBr(CO)3(N,N′-Phd-O,O′)Y(OTf)3.

Trichlorostannyl complex Co(SnCl3)(CO)2(PPh3)2 (1) was prepared by allowing the chloro compound CoCl(CO)2(PPh3)2 to react with SnCl2·2H2O. Instead, treatment of the iodo complex CoI(CO)2[PPh(OEt)2]2 with SnCl2·2H2O afforded a mixture of Co(SnCl2I)(CO)2[PPh(OEt)2]2 (2a) and Co(SnCl3)(CO)2[PPh(OEt)2]2 (2b) derivatives. Trichlorogermyl complexes Co(GeCl3)(CO)2L2 (3, 4) [L = PPh3, PPh(OEt)2] were prepared by allowing halo compounds CoX(CO)2L2 (X = Cl, I) to react with GeCl2·dioxane. Treatment of trihalostannyl complexes Co(SnCl2X)(CO)2L2 (1, 2) (X = Cl, I) with NaBH4 in ethanol yielded tin trihydrido derivatives Co(SnH3)(CO)2L2 (5, 6). Instead, reaction of Co(SnCl2X)(CO)2[PPh(OEt)2]2 (2) with LiAlH4 in THF yielded the hydrido CoH(CO)2[PPh(OEt)2]2 (7). Trimethylstannyl Co(SnMe3)(CO)2L2 (8, 9) and trialkynylstannyl derivatives Co[Sn(C CPh)3](CO)2L2 (10, 11) were prepared by allowing trihalostannyl compounds Co(SnCl2X)(CO)2L2 (1, 2) to react with MgBrMe and with Li+(PhC C)−, respectively, in THF. The complexes were characterised by spectroscopy (IR and 1H, 31P, 13C, 119Sn NMR) and by X-ray crystal structure determination of Co(SnCl2X)(CO)2[PPh(OEt)2]2 (2) and Co(GeCl3)(CO)2[PPh(OEt)2]2 (4).

Nitrosyl complexes [M(CO) 3 (NO)L 2 ]BPh 4 ( 2 , 5 ) [M = Mo, W; L = PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing carbonyl compounds M(CO) 4 L 2 ( 1 , 4 ) to react with NOPF 6 in CH 2 Cl 2 . Dicarbonyl complex [W(CO) 2 (NO){PPh(OEt) 2 } 3 ]BPh 4 ( 7 ) was also prepared by reacting W(CO) 3 [PPh(OEt) 2 ] 3 ( 6 ) with NOPF 6 . Treatment of nitrosyl complexes 2 , 5 with [NEt 4 ]Br gave bromide derivative [MBr(CO) 2 (NO)L 2 ]BPh 4 ( 3 ). Hydrazine complexes [M(CO)(RNHNH 2 )(NO)L 3 ]BPh 4 ( 8 , 9 , 10 ) (R = H, CH 3 ) were prepared by allowing nitrosyl complexes 2 , 5 to react with hydrazine RNHNH 2 in CH 2 Cl 2 . Reaction of methylhydrazine complexes [M(CO)(CH 3 NHNH 2 )(NO)L 3 ]BPh 4 ( 8 , 10 ) with Pb(OAc) 4 at −30 °C resulted in selective oxidation of hydrazine, affording the corresponding methyldiazene derivatives [M(CO)(CH 3 N NH)(NO)L 3 ]BPh 4 ( 11 , 12 ). The complexes were characterised spectroscopically (IR and NMR), and a geometry in solution was also established.

Ethylene complexes [OsCl(η6-p-cymene)(η2-CH2 CH2)L]BPh4 (1, 2) [L = P(OMe)3, P(OEt)3, PPh(OEt)2, tBuNC) were prepared by allowing the dichloro compounds OsCl2(η6-p-cymene)L to react with CH2 CH2 in mild conditions (1 atm). Treatment of 1 with amine or hydrazine yielded [OsCl(p-tolyl-NH2)(η6-p-cymene){PPh(OEt)2}]BPh4 (3) or [OsCl(η6-p-cymene)(CH3NHNH2){PPh(OEt)2}]BPh4 (4) derivatives. The vinylidene cation [OsCl{ C C(H)Ph}(η6-p-cymene){PPh(OEt)2}]+ (5+) was also prepared from 1 and PhC CH. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [OsCl(η6-p-cymene)(η2-CH2 CH2){P(OMe)3}]BPh4 (1a). The nature of the Os–ethylene bond was investigated from a computational point of view.

Hydrazine complexes [MCl(η 6 - p -cymene)(RNHNH 2 )L]BPh 4 ( 1 – 6 ) [M = Ru, Os; R = H, Me, Ph; L = P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing dichloro complexes MCl 2 (η 6 - p -cymene)L to react with hydrazines RNHNH 2 in the presence of NaBPh 4 . Treatment of ruthenium complexes [RuCl(η 6 - p -cymene)(RNHNH 2 )L]BPh 4 with Pb(OAc) 4 led to acetate complex [Ru(κ 2 –O 2 CCH 3 )(η 6 - p -cymene)L]BPh 4 ( 7 ). Instead, the reaction of osmium derivatives [OsCl(η 6 - p -cymene)(CH 3 NHNH 2 )L]BPh 4 with Pb(OAc) 4 afforded the methyldiazenido complex [Os(CH 3 N 2 )(η 6 - p -cymene)L}]BPh 4 ( 8 ). Treatment with HCl of this diazenido complex 8 led to the methyldiazene cation [OsCl(CH 3 N NH)(η 6 - p -cymene)L}] + ( 9 + ). The complexes were characterised spectroscopically and by X-ray crystal structure determination of [OsCl(η 6 - p -cymene)(PhNHNH 2 ){PPh(OEt) 2 }]BPh 4 ( 6b ) and [Ru(κ 2 –O 2 CCH 3 )(η 6 - p -cymene){PPh(OEt) 2 }]BPh 4 ( 7b ).

Trichlorogermyl complexes M(GeCl 3 )(CO) n P 5− n ( 1–4 ) [M = Mn, Re; n = 2, 3; P = PPh(OEt) 2 ( a ), P(OEt) 3 ( b )] were prepared by allowing chloro compounds MCl(CO) n P 5− n to react with an excess of GeCl 2 •dioxane in 1,2-dichloroethane. Treatment of compounds 1–4 with LiAlH 4 in thf yielded trihydridegermyl derivatives M(GeH 3 )(CO) n P 5− n ( 5–8 ), whereas treatment of the same complexes with NaBH 4 in ethanol afforded triethoxygermyl derivatives M[Ge(OEt) 3 ](CO) n P 5− n ( 9–11 ). Trimethylgermyl compounds M(GeMe 3 )(CO) n P 5− n ( 12, 13 ) and the alkynylgermyl derivative Mn[Ge(C CPh) 3 ](CO) 3 [PPh(OEt) 2 ] 2 ( 14a ) were also prepared by allowing trichlorogermyl compounds 1–4 to react with either MgBrMe or Li + C CPh − , respectively, in thf. Treatment of compound Re(GeCl 3 )(CO) 3 [PPh(OEt) 2 ] 2 ( 4a ) with SnCl 2 •2H 2 O gave the stannyl-germyl derivative Re[GeCl 2 (SnCl 3 )](CO) 3 [PPh(OEt) 2 ] 2 ( 15a ). The complexes were characterised by spectroscopy and X-ray crystal structure determination of 4a , 5a , and 13a .

Pyrazole (HRpz) [MCl(η6-p-cymene)(HRpz)L]BPh4 (1–8) and imidazole (HIm) complexes [MCl(η6-p-cymene)(HIm)L]BPh4 (9–10) [M = Ru, Os; R = H, 3-Me, 3,5-Me2; L = P(OEt)3, PPh(OEt)2, PPh2OEt, CNtBu] were prepared by allowing the dichloro compounds MCl2(η6-p-cymene)L to react with the appropriate azole in the presence of NaBPh4. Treatment of the dichloro complexes with an excess of both pyrazole and NEt3 yielded the pyrazole–pyrazolate derivatives [M(Rpz)(η6-p-cymene)(HRpz)L]BPh4 (11–14). Conversely, the reaction of carbonyl compounds RuCl2(η6-p-cymene)(CO) with pyrazole or imidazole yielded the bisazole complexes [MCl(η6-p-cymene)(HRpz)2]BPh4 or [MCl(η6-p-cymene)(HIm)2]BPh4 (15–17). The complexes were characterised spectroscopically (IR and 1H, 13C, 31P NMR) and by X-ray crystal structure analysis [RuCl(η6-p-cymene)(HRpz){PPh(OEt)2}]BPh4 (1b), [Ru(pz)(η6-p-cymene)(HRpz){P(OEt)3}]BPh4 (11a) and [RuCl(η6-p-cymene)(HRpz)2]BPh4 (15).

p-Cymene complexes MCl2(η6-p-cymene)L [M = Ru, Os; L = P(OEt)3, PPh(OEt)2, (CH3)3CNC] were prepared by allowing [MCl(μ-Cl)(η6-p-cymene)]2 to react with phosphites or tert-butyl isocyanide. Treatment of MCl2(η6-p-cymene)L complexes with 1,3-ArN NN(H)Ar triazene and an excess of NEt3 gave the cationic triazenide derivatives [M(η2-1,3-ArNNNAr)(η6-p-cymene)L]BPh4 (Ar = Ph, p-tolyl). Neutral triazenide complexes MCl(η2-1,3-ArNNNAr)(η6-p-cymene) (M = Ru, Os) were also prepared by allowing [MCl(μ-Cl)(η6-p-cymene)]2 to react with 1,3-diaryltriazene in the presence of triethylamine. p-Cymene complexes MCl2(η6-p-cymene)L reacted with equimolar amounts of 1,3-ArN NN(H)Ar triazene to give both triazenide complexes [M(η2-1,3-ArNNNAr)(η6-p-cymene)L]BPh4 and amine derivatives [MCl(ArNH2)(η6-p-cymene)L]BPh4. A reaction path for the formation of the amine complex is also reported. The complexes were characterised by spectroscopy and X-ray crystallography of RuCl2(η6-p-cymene)[PPh(OEt)2] and [Ru(η2-1,3-p-tolyl-NNN-p-tolyl)(η6-p-cymene){CNC(CH3)3}]BPh4. Selected triazenide complexes were studied as catalysts in the hydrogenation of 2-cyclohexen-1-one and cinnamaldehyde.

Cyanoguanidine complexes [MCl{η 1 -N≡CN(H)C(NH 2 )=NH}-(η 6 -p-cymene)(PR 3 )]BPh 4 [M = Ru, Os; PR 3 = P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt, PiPr 3 ] were prepared by treating compounds [MCl 2 (η 6 -p-cymene)(PR3)] with cyanamide N≡CNH 2 . Alternatively, complexes [MCl(η 1 -N≡CN(H)C-(NH 2 )=NH}(η 6 -p-cymene)(PR 3 )]BPh 4 were prepared by treating [MCl 2 (η 6 -p-cymene)(PR 3 )] with cyanoguanidine. Diethyl-cyanamide complexes [MCl(N≡CNEt 2 )(η 6 -p-cymene)(PR 3 )]-BPh 4 were also obtained by treating [MCl 2 (η 6 -p-cymene)-(PR 3 )] with an excess amount of N≡CNEt 2 . Complexes were characterised spectroscopically (IR, 1 H, 31 P, 13 C NMR) and in the case of [RuCl{N≡CN(H)C(NH 2 )=NH}(η 6 -p-cymene)-(PPh(OEt) 2 }]BPh 4 by X-ray crystal structure determination.

Diazoalkane complexes [RuCl(N2CAr1Ar2)(η6-p-cymene)P]BPh4 [Ar1 = Ph; Ar2 = Ph or p-tolyl; P = PPh(OEt)2 or P(OEt)3] were prepared by allowing p-cymene complexes RuCl2(η6-p-cymene)P to react with di...

The complexes [Re2{Sn2(μ-S)(μ-SO3)2}(CO)4L2{PPh(OEt)2}4] (L = PPh(OEt)2 (1), (CH3)3CNC (2)) were prepared by reaction of the trihydridostannyl compounds Re(SnH3)(CO)2L[PPh(OEt)2]2 with SO2 under mi...

Trichlorostannyl complexes M(SnCl3)(Tp)L(PPh3) (1, 2) and M(SnCl3)(Cp)L(PPh3) (5, 6) [M = Ru, Os; L = P(OMe)3 (a), P(OEt)3 (b), PPh(OEt)2 (c), PPh3 (d)] were prepared by allowing chloro complexes MCl(Tp)L(PPh3) and MCl(Cp)L(PPh3) to react with an excess of SnCl2·2H2O in ethanol. Treatment of trichlorostannyl complexes 1, 2, 5, and 6 with NaBH4 in ethanol yielded tin trihydride derivatives M(SnH3)(Tp)L(PPh3) (3, 4) and M(SnH3)(Cp)L(PPh3) (7, 8). Reaction of these complexes with CCl4 gave the trichlorostannyl precursors 1, 2, 5, and 6. Hydridochlorostannyl intermediates Os(SnH2Cl)(Tp)[P(OMe)3](PPh3) (9a) and Os(SnHCl2)(Tp)[P(OMe)3](PPh3) (10a) were also obtained. Reaction of trihydridostannyl complexes M(SnH3)(Tp)L(PPh3) (3, 4) with CO2 (1 atm) led to hydridobis(formate) derivatives M[SnH{OC(H)═O}2](Tp)L(PPh3) (11). In contrast, reaction of the related complexes M(SnH3)(Cp)L(PPh3) (7, 8) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [M[Sn{OC(H)═O}2(μ-OH)](Cp)L(PPh3)]2 (12, 13). ...

Trivinylstannyl complexes Re[Sn{C(COOR)═CH2}3](CO)2L3 (1, 2) and M[Sn{C(COOR)═CH2}3](CO)3L2 (3, 4) [M = Re, Mn; R = Me, Et; L = P(OEt)3, PPh(OEt)2] were prepared by allowing trihydridostannyl complexes Re(SnH3)(CO)2L3 and M(SnH3)(CO)3L2 to react with alkyl propiolates. The complexes were characterized spectroscopically (IR, 1H, 31P, 13C, 119Sn NMR) and by X-ray crystal structure determination of Re[Sn{C(COOMe)═CH2}3](CO)2[P(OEt)3]3 (1a). Reaction of trivinylstannyl complex 1a with HCl resulted in cleavage of one vinyl group to give (chlorodivinyl)stannyl derivative Re[SnCl{C(COOMe)═CH2}2](CO)2[P(OEt)3]3 (6a).

Hydride complex RuH 2 (PFFP) 2 ( 1 ) [PFFP = (CF 3 CH 2 O) 2 PN(CH 3 )N(CH 3 )P(OCH 2 CF 3 ) 2 ] was prepared by allowing the compound RuCl 4 (bpy) · H 2 O (bpy = 1,2-bipyridine) to react first with the phosphite PFFP and then with NaBH 4 . Chloro-complex RuCl 2 (PFFP) 2 ( 2 ) was also prepared, either by reacting RuCl 4 (bpy) · H 2 O with PFFP and zinc dust or by substituting triphenylphosphine with PFFP in the precursor complex RuCl 2 (PPh 3 ) 3 . Hydride derivative RuH 2 (POOP) 2 ( 3 ) (POOP = Ph 2 POCH 2 CH 2 OPPh 2 ) was prepared by reacting compound RuCl 3 (AsPh 3 ) 2 (CH 3 OH) first with the phosphite POOP and then with NaBH 4 . Depending on experimental conditions, treatment of carbonylated solutions of RuCl 3 · 3H 2 O with POOP yields either the cis - or trans -RuCl 2 (CO)(PHPh 2 )(POOP) ( 4 ) derivative. Reaction of both cis - and trans - 4 with LiAlH 4 in thf affords dihydride complex RuH 2 (CO)(PHPh 2 )(POOP) ( 5 ). Chloro-complex all - trans -RuCl 2 (CO) 2 (PPh 2 OMe) 2 ( 6 ) was obtained by reacting carbonylated solutions of RuCl 3 · 3H 2 O in methanol with POOP. Treatment of chloro-complex 6 with NaBH 4 in ethanol yielded hydride derivative all - trans -RuH 2 (CO) 2 (PPh 2 OMe) 2 ( 7 ). The complexes were characterised spectroscopically and the X-ray crystal structures of complexes 1 , 3 , cis - 4 and 6 were determined.

Mixed-ligand OsCl(Tp)L(PPh3) complexes 1 [Tp = hydridotris(pyrazolyl)borate; L = P(OMe)3, P(OEt)3 and PPh(OEt)2] were prepared by allowing OsCl(Tp)(PPh3)2 to react with an excess of phosphite. Treatment of chlorocomplexes 1 with NaBH4 in ethanol afforded hydride OsH(Tp)L(PPh3) derivatives 2. Stable dihydrogen [Os(η2-H2)(Tp)L(PPh3)]BPh4 derivatives 3 were prepared by protonation of hydrides 2 with HBF4 · Et2O at −80 °C. The presence of the η2-H2 ligand is supported by short T1 min values and JHD measurements on the partially deuterated derivatives. Treatment of the hydride OsH(Tp)[P(OEt)3](PPh3) complex with the aryldiazonium salt [4-CH3C6H4N2]BF4 afforded aryldiazene [Os(4-CH3C6H4NNH)(Tp){P(OEt)3}(PPh3)]BPh4 derivative 4. Instead, aryldiazenido [Os(4-CH3C6H4N2)(Tp)[P(OEt)3](PPh3)](BF4)2 derivative 5 was obtained by reacting the hydride OsH(Tp)[P(OEt)3](PPh3) first with methyltriflate and then with aryldiazonium [4-CH3C6H4N2]BF4 salt. Spectroscopic characterisation (IR, 15N NMR) by the 15N-labelled derivative strongly supports the presence of a near-linear Os–NN–Ar aryldiazenido group. Imine [Os{η1-NHC(H)Ar}(Tp){P(OEt)3}(PPh3)]BPh4 complexes 6 and 7 (Ar = C6H5, 4-CH3C6H4) were also prepared by allowing the hydride OsH(Tp)[P(OEt)3](PPh3) to react first with methyltriflate and then with alkylazides.

The trichlorostannyl complexes M(SnCl3)(CO)nP5-n (1−3: M = Mn, Re; P = PPh(OEt)2 (a), P(OEt)3 (b); n = 2, 3) were prepared by allowing chloro MCl(CO)nP5-n compounds to react with an excess of SnCl2·2H2O. Treatment of compounds 1−3 with NaBH4 in ethanol yielded the tin polyhydride derivatives M(SnH3)(CO)nP5-n (4−6). Treatment of 1−3 with MgBrMe gave the trimethylstannyl complexes M(SnMe3)(CO)nP5-n (7−9), and the reaction of 1−3 with MgBr(C⋮CH) yielded the trialkynylstannyl derivatives M[Sn(C⋮CH)3](CO)nP5-n (10, 11). The alkynylstannyl complexes M[Sn(C⋮CR)3](CO)nP5-n (12−14: R = p-tolyl) were also prepared by allowing M(SnCl3)(CO)nP5-n compounds to react with Li+[C⋮CR]- in thf. The complexes were characterized by spectroscopy and by X-ray crystal structure determinations of 4a, 6b, and 9b. Reaction of the tin trihydride complexes Re(SnH3)(CO)2P3 (6) with CO2 (1 atm) led to the binuclear OH-bridging bis(formate) derivatives [Re{Sn[OC(H)O]2(μ-OH)}(CO)2P3]2 (15). A reaction path for the formation of 15, invo...

The hydrido complexes [ReH(Cl)(N-N)P 3 ]BPh 4 [P = PPh-(OEt) 2 ; N-N = 2,2'-bipyridine (bpy), 5,5'-dimethylbipyridine (5,5'-Me 2 bpy), 1,10-phenanthroline (phen)] have been prepared by allowing ReCl 3 P 3 to react with the polypyridine in refluxing ethanol. The dihydrido [ReH 2 (bpy)P 3 ]BPh 4 complex has also been prepared by treating [ReHCl(bpy)P 3 ] + cation with NaBH 4 in ethanol. Similarly, the hydrido tricarbonyl derivative [ReH 2 (bpy)(CO) 3 ]BPh 4 has been synthesized by allowing [ReH(bpy)(CO) 3 ] to react with HBF 4 ·Et 2 O. All complexes have been characterized spectroscopically (IR and NMR spectroscopic data) and the [ReHCl(bpy){PPh-(OEt) 2 } 3 ]BPh 4 derivative by X-ray crystallography. Protonation of both [ReHCl(bpy)P 3 ]BPh 4 and [ReH 2 (bpy)P 3 ]BPh 4 with HBF 4 ·Et 2 O leads to the classical cations [ReH 2 Cl-(bpy)P 3 ] 2+ and [ReH 3 (bpy)P 3 ] 2+ , respectively. The vinyl complexes [Re{CH=C(H)R)2(bpy)P3]BPh4 (R = Ph, p-tolyl, tert-butyl) have also been prepared by allowing the dihydrido derivative [ReH 2 (bpy)P 3 ]BPh 4 to react with an excess of terminal alkyne in 1,2-dichloroethane.

Diazoalkane complexes [Ru(Tp)(N2CAr1Ar2)(PPh3)L]BPh4 ( and ) [Tp = tris(pyrazolyl)borate; L = P(OMe)3, P(OEt)3; Ar1 = Ar2 = Ph; Ar1 = Ph, Ar2 = p-tolyl; Ar1Ar2 = C12H8] were prepared by allowing chloro-compounds RuCl(Tp)(PPh3)L to react with diazoalkane in the presence of NaBPh4. Acrylonitrile CH2[double bond, length as m-dash]C(H)CN reacts with diazoalkane complexes to give 3H-pyrazole derivatives [Ru(Tp){N[double bond, length as m-dash]NC(Ar1Ar2)CH(CN)CH2}(PPh3){P(OMe)3}]BPh4 and [Ru(Tp){N[double bond, length as m-dash]NC(Ar1Ar2)CH2C(H)CN}(PPh3){P(OMe)3}]BPh4 (). Diazoalkane complexes [Ru(bpza)(N2CAr1Ar2)(PPh3)2]BPh4 () [bpza = bis(pyrazolyl)acetate] were also prepared. All complexes were characterised by IR and NMR spectroscopy and X-ray crystal structure determination of [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}]BPh4 (). The differences exhibited by [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}](+) and [Ru(Cp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}](+), as regards coordination of the diazoalkane ligand and reactivity towards alkenes, were explained on the basis of a comparative DFT study.

Vinylidene complexes [Ru(η(5)-C5H5){[double bond, length as m-dash]C[double bond, length as m-dash]C(H)R}(PPh3)L]BPh4 (, ) [L = P(OMe)3, P(OEt)3; R = Ph, p-tolyl, Bu(t), H] react with hydrazine R1NHNH2 (R1 = H, Me, Ph) to afford nitrile derivatives [Ru(η(5)-C5H5)(N[triple bond, length as m-dash]CCH2R)(PPh3)L]BPh4 (, ) and amine R1NH2. Hydroxylamine NH2OH also reacts with vinylidenes , to yield nitrile derivatives , and H2O. Studies with (15)N-labeled hydrazine and DFT calculations allowed a reaction path to be proposed. The complexes were characterized by spectroscopy (IR, (1)H, (31)P, (13)C and (15)N NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5H5)(N[triple bond, length as m-dash]CCH2Ph)(PPh3){P(OEt)3}]BPh4 ().

The reaction of the chloro-complex RuCl(η(5)-C5H5)(PPh3)[P(OMe)3] with alkylpropiolates HC≡CCOOR1 in alcohol R2OH affords pyranylidene derivatives [Ru(η(5)-C5H5){=C(COOR1)C(H)C(H)C(OR1)O}(PPh3){P(OMe)3}]BPh4 (1, 3) and alkoxycarbene complexes [Ru(η(5)-C5H5){=C(OR2)(CH2COOR1)}(PPh3){P(OMe)3}]BPh4 (2, 4). A reaction path for the formation of compounds 1-4, involving reactions on a vinylidene intermediate complex, is also discussed. The complexes were characterized spectroscopically (IR and (1)H, (13)C, (31)P NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5H5){=C(COOMe)C(H)C(H)C(OMe)O}(PPh3){P(OMe)3}]BPh4 (1).

Diazoalkane complexes [Ru(η(5)-C5Me5)(N2CAr1Ar2)(PPh3){P(OR)3}]BPh4 [R = Me (1), Et (2); Ar1 = Ar2 = Ph (a); Ar1 = Ph, Ar2 = p-tolyl (b); Ar1Ar2 = C12H8 (c)] were prepared by allowing chloro complexes RuCl(η(5)-C5Me5)(PPh3)[P(OR)3] to react with diazoalkane Ar1Ar2CN2 in ethanol. The treatment of compounds 1 and 2 with H2O afforded 1,2-diazene derivatives [Ru(η(5)-C5Me5)(η(2)-NH═NH)(PPh3){P(OR)3}]BPh4 (3 and 4) and ketone Ar1Ar2CO. A reaction path involving nucleophilic attack by H2O on the coordinated diazoalkane is proposed. The complexes were characterized spectroscopically (IR and NMR) and by X-ray crystal structure determination of [Ru(η(5)-C5Me5)(η(2)-NH═NH)(PPh3){P(OMe)3}]BPh4 (3).

Pyrazole IrHCl 2 (HRpz)P 2 [P = PPh 3 , P i Pr 3 ; R = H, 3-Me], bis(pyrazole) [IrHCl(HRpz) 2 (PPh 3 ) 2 ]BPh 4 and imidazole IrHCl 2 (HIm)(PPh 3 ) 2 derivatives were prepared by allowing the IrHCl 2 (PPh 3 ) 3 complex to react with the appropriate azole in refluxing 1,2-dichloroethane. Nitrile IrHCl 2 (CH 3 CN)(PPh 3 ) 2 and 2,2′-bipyridine (bpy) [IrHCl(bpy)(PPh 3 ) 2 ]BPh 4 derivatives were also prepared using IrHCl 2 (PPh 3 ) 3 as a precursor. The complexes were characterised spectroscopically (IR and NMR) and a geometry in solution was also established. Protonation with Bronsted acid of pyrazole IrHCl 2 (Hpz)(PPh 3 ) 2 and imidazole IrHCl 2 (HIm)(PPh 3 ) 2 complexes proceeded with the loss of the azole ligands and the formation of the unstable IrHCl 2 (PPh 3 ) 2 derivative. Vinyl IrCl 2 {CH C(H)R1}(HRpz)P 2 and IrCl 2 {CH C(H)R1}(HIm)P 2 (R1 = Ph, p- tolyl, COOCH 3 ; P = PPh 3 , P i Pr 3 ) complexes were prepared by allowing hydride-pyrazole IrHCl 2 (HRpz)P 2 and hydride-imidazole IrHCl 2 (HIm)P 2 to react with an excess of terminal alkyne in 1,2-dichloroethane. The complexes were characterised spectroscopically and by the X-ray crystal structure determination of the IrCl 2 {CH C(H)Ph}(Hpz)(PPh 3 ) 2 derivative.

Dithioformato [Re{η 2 -SC(H)S}(NO)P 3 ]BPh 4 ( 1 ), thioformamido [Re{η 2 -RNC(H)S}(NO)P 3 ]BPh 4 ( 2 ) (R = Et, p -tolyl), formamido [Re{η 2 -PhNC(H)O}(NO)P 3 ]BPh 4 ( 3 ) and formamidinato [Re{η 2 - p -tolylNC(H)N p -tolyl}(NO)P 3 ]BPh 4 ( 4 ) (P = PPh 2 OEt) complexes were prepared by allowing the hydride ReH 2 (NO)P 3 to react first with triflic acid and then with the appropriate heteroallene CS 2 , RNCS, PhNCO and p -tolylNCN p -tolyl. Treatment of the ReH 2 (NO)L(PPh 3 ) 2 [L = P(OEt) 3 , PPh(OEt) 2 ] and ReH 2 (NO)(PPh 3 ) 3 hydrides first with triflic acid and then with isothiocyanate RNCS (R = Et, p -tolyl) gave the [Re{η 2 -RNC(H)S}(NO){P(OEt) 3 }(PPh 3 ) 2 ]BPh 4 ( 5 , 6 ) and [Re(η 2 -RNC(H)S)(NO)(PPh 3 ) 3 ]BPh 4 ( 7 ) derivatives. Depending on the nature of the phosphite, instead, the reaction of ReH 2 (NO)L(PPh 3 ) 2 and ReH 2 (NO)(PPh 3 ) 3 hydrides first with CF 3 SO 3 H and then with isocyanate R1NCO (R1 = Ph, p -tolyl) gave the chelate [Re{η 2 -R1NC(H)O}(NO){P(OEt) 3 }(PPh 3 ) 2 ]BPh 4 ( 8 ) and [Re{η 2 -R1NC(H)O}(NO)(PPh 3 ) 3 ]BPh 4 ( 10 ) complexes with P(OEt) 3 or PPh 3 , while the η 1 -coordinate [Re{η 1 -RNC(H)S}(NO){PPh(OEt) 2 } 2 (PPh 3 ) 2 ]BPh 4 ( 9 ) derivative was obtained with the PPh(OEt) 2 phosphite ligand. η 1 -Coordinate dithioformato [Re{η 1 -SC(H) S}(NO){PPh(OEt) 2 } 2 (PPh 3 ) 2 ]BPh 4 ( 11 ) and formato [Re{η 1 -OC(H) O}(NO){PPh(OEt) 2 } 2 (PPh 3 ) 2 ]BPh 4 ( 12 ) complexes, as well as the formamidinato [Re{η 2 - p -tolylNC(H)N p -tolyl}(NO){P(OEt) 3 }(PPh 3 ) 2 ]BPh 4 ( 13 ) derivative were also prepared.

Chloro phosphite complexes RuClTpL(PPh 3 ) ( 1a , 1b ) [L = P(OEt) 3 , PPh(OEt) 2 ] and RuClTp[P(OEt) 3 ] 2 ( 1c ) [Tp = hydridotris(pyrazolyl)borate] were prepared by allowing RuClTp(PPh 3 ) 2 to react with an excess of phosphite. Treatment of the chloro complexes 1 with NaBH 4 in ethanol yielded the hydride RuHTpL(PPh 3 ) ( 2a , 2b ) and RuHTp[P(OEt) 3 ] 2 ( 2c ) derivatives. Protonation reaction of 2 with Bronsted acids was studied and led to thermally unstable (above 10 °C) dihydrogen [Ru(η 2 - H 2 )TpL(PPh 3 )] + ( 3a , 3b ) and [Ru(η 2 -H 2 )Tp{P(OEt) 3 } 2 ] + ( 3c ) complexes. The presence of the η 2 -H 2 ligand is indicated by short T 1 min values and J HD measurements of the partially deuterated derivatives. Aquo [RuTp(H 2 O)L(PPh 3 )]BPh 4 ( 4 ), carbonyl [RuTp(CO)L(PPh 3 )]BPh 4 ( 5 ), and nitrile [RuTp(CH 3 CN)L(PPh 3 )]BPh 4 ( 6 ) derivatives [L = P(OEt) 3 ] were prepared by substituting H 2 in the η 2 -H 2 derivatives 3 . Vinylidene [RuTp{ C C(H)R}L(PPh 3 )]BPh 4 ( 7 , 8 ) (R = Ph, t Bu) and allenylidene [RuTp( C C CR1R2)L(PPh 3 )]BPh 4 ( 9 – 11 ) complexes (R1 = R2 = Ph, R1 = Ph R2 = Me) were also prepared by allowing dihydrogen complexes 3 to react with the appropriate HC CR and HC CC(OH)R1R2 alkynes. Deprotonation of vinylidene complexes 7 , 8 with NEt 3 was studied and led to acetylide Ru(C CR)TpL(PPh 3 ) ( 12 , 13 ) derivatives. The trichlorostannyl Ru(SnCl 3 )TpL(PPh 3 ) ( 14 ) compound was also prepared by allowing the chloro complex RuClTpL(PPh 3 ) to react with SnCl 2 · 2H 2 O in CH 2 Cl 2 .