Search

The borane dimethyl sulfide adduct H3B·SMe2 and the diethyl ether adduct of tris(pentafluorophenyl)borane, (C6F5)3B·OEt2, undergo facile exchange of hydride and pentafluorophenyl ligands, yielding (C6F5)2HB·SMe2 (1) and (C6F5)H2B·SMe2 (2) depending upon the ratio of reagents used. In the presence of excess dimethyl sulfide, both compounds can be isolated as colorless crystals, which have been structurally characterized.

The phosphinoborane adduct H(3)P x B(C(6)F(5))(3) can be deprotonated using LiN(SiMe(3))(2) to give the phosphidoborate salt Li[H(2)PB(C(6)F(5))(3)], which was converted to the phosphidodiborates Li[H(2)P{B(C(6)F(5))(3)}(2)] and Li[H(2)P{B(C(6)F(5))(3)}{BH(3)}] by treatment with an equivalent of B(C(6)F(5))(3) or Me(2)S.BH(3), respectively. A series of anions of the form [RR'P{M(C(6)F(5))(3)}{BH(3)}](-), where R = R' = Ph or R= (t)Bu, R' = H, and M = B or Al, were prepared (through treatment of salts Li[RR'P(BH(3))] with the corresponding Lewis acid) and characterized using multinuclear NMR, elemental analysis and X-ray crystallography. The solid state structures of [Li(Et(2)O)(x)][Ph(2)P{M(C(6)F(5))(3)}{BH(3)}] exhibit eta(2)-bonding of the BH(3) group to the cationic lithium center. The attempted preparation of an analogous series with amide cores of the form [R(2)N{B(C(6)F(5))(3)}{BH(3)}](-) proved unsuccessful; among the competing reaction pathways hydride abstraction occurred preferentially to yield Li[HB(C(6)F(5))(3)] and dimers or higher oligomers with the composition (R(2)NBH(2))(n).

The reactions of MCl or MOCl with imidazole-based pro-ligand LH, 3,5-tBu-2-OH-CH -(4,5-Ph-1H-)imidazole, or oxazole-based ligand L H, 3,5-tBu-2-OH-CH(1H- phenanthro[9,10-d])oxazole, following work-up, afforded octahedral complexes [MX(L)], where MX=NbCl (L, 1 a; L , 2 a), [NbOCl(NCMe)] (L, 1 b; L , 2 b), TaCl (L, 1 c; L, 2 c), or [TaOCl(NCMe)] (L, 1 d). The treatment of α-diimine ligand L, (2,6-iPrCH N=CH), with [MCl(thf)] (M=Nb, Ta) afforded [MCl(L)] (M=Nb, 3 a; Ta, 3 b). The reaction of [MCl(dme)] (dme=1,2-dimethoxyethane; M=Nb, Ta) with bis(imino)pyridine ligand L, 2,6-[2,6-iPrC HN=(Me)C]CHN, afforded known complexes of the type [MCl(L)] (M=Nb, 4 a; Ta, 4 b), whereas the reaction of 2-acetyl-6-iminopyridine ligand L , 2-[2,6-iPrCHN=(Me)C]-6-Ac- CHN, with the niobium precursor afforded the coupled product [({2-Ac-6-(2,6-iPrCHN=(Me)C)C HN}NbOCl)] (5). The reaction of MCl with Schiff-base pro-ligands LH-LH, 3,5-(R)-2-OH-CHCH=N(2-OR -CH), (LH: R=tBu, R=Ph; LH: R=tBu, R=Me; L H: R=Cl, R=Ph; LH: R =Cl, R=Me; LH: R=Cl, R =CF) afforded [MCl(L)] complexes (M=Nb, 6 a-10 a; M=Ta, 6 b-9 b). In the case of compound 8 b, the corresponding zwitterion was also synthesised, namely [TaCl (LH)]×MeCN (8 c). Unexpectedly, the reaction of LH with TaCl at reflux in toluene led to the removal of the methyl group and the formation of trichloride 7 c [TaCl (L)]; conducting the reaction at room temperature led to the formation of the expected methoxy compound (7 b). Upon activation with methylaluminoxane (MAO), these complexes displayed poor activities for the homogeneous polymerisation of ethylene. However, the use of chloroalkylaluminium reagents, such as dimethylaluminium chloride (DMAC) and methylaluminium dichloride (MADC), as co-catalysts in the presence of the reactivator ethyl trichloroacetate (ETA) generated thermally stable catalysts with, in the case of niobium, catalytic activities that were two orders of magnitude higher than those previously observed. The effects of steric hindrance and electronic configuration on the polymerisation activity of these tantalum and niobium pre-catalysts were investigated. Spectroscopic studies (H NMR, C NMR and H-H and H- C correlations) on the reactions of compounds 4 a/4 b with either MAO(50) or AlMe/[CPh][B(CF )] were consistent with the formation of a diamagnetic cation of the form [LAlMe] (MAO(50) is the product of the vacuum distillation of commercial MAO at +50 °C and contains only 1 mol % of Al in the form of free AlMe). In the presence of MAO, this cationic aluminium complex was not capable of initiating the ROMP (ring opening metathesis polymerisation) of norbornene, whereas the 4 a/4 b systems with MAO(50) were active. A parallel pressure reactor (PPR)-based homogeneous polymerisation screening by using pre-catalysts 1 b, 1 c, 2 a, 3 a and 6 a, in combination with MAO, revealed only moderate-to-good activities for the homo-polymerisation of ethylene and the co-polymerisation of ethylene/1-hexene. The molecular structures are reported for complexes 1 a-1 c, 2 b, 5, 6 a, 6 b, 7 a, 8 a and 8 c. Ta very much: The combination of a niobium or tantalum pre-catalyst that contains an imine-based ligand set and a MeAlCl (MADC) co-catalyst is capable, in the presence of ethyl trichloroacetate (ETA), of polymerising ethylene with activities in excess of 11 000 g mmol h bar for niobium and 20 000 g mmol h bar for tantalum. These systems produced essentially linear, high-molecular-weight polyethylene.

The structures of three novel compounds prepared from the reaction of the lower-rim 1,3-diacid calix[4]arene (LH(2)) with lithium carbonate (1), t-butyl-lithium (2) and zinc acetate (3) are reported.

Treatment of TiCl(NMe(2))(3) with H(3)N·B(C(6)F(5))(3) results in N-H activation and ligand exchange to yield the structurally characterised salt [TiCl(NMe(2))(2)(NMe(2)H)(2)](+)[Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-). Cation exchange with [Me(4)N]Cl, [Ph(4)P]Cl and [(PhCH(2))Ph(3)P]Cl yields the respective ammonium and phosphonium salts of the [Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-) anion. X-ray crystallography reveals that the essential trigonal bipyramidal geometry and composition of the anion is retained in each of these salts despite some minor variations in the Ti-N-B angle and the nature of the interionic interactions. Electronic investigation by DFT calculations confirmed the Ti-N triple bond character implied by the experimentally determined bond length, with the HOMO and HOMO-1 having Ti-N π-bonding character. The dimethylamine ligands of the anion resist substitution by moderate bases but can be displaced by pyridine to give a pentacoordinate anion. In contrast, addition of 2,2'-bipyridyl gives a neutral octahedral complex. Treatment of the pyridine complex with TlCp results in the formation of a four coordinate anionic cyclopentadienyl complex.

Treatment of the tris(pyrazolyl)borate metal triamides Tp'M(NMe(2))(3), where Tp' = (C(3)H(3)N(2))(3)BH (Tp) or (3,5-Me(2)C(3)HN(2))(3)BH (Tp*) and M = Ti, Zr and Hf, with the Brønsted acidic Lewis adduct (C(6)F(5))(3)B·NH(3) in toluene solution leads to the formation of Tp'M(NMe(2))(2){NH(2)B(C(6)F(5))(3)} complexes. The exception to this was the attempted preparation of Tp*Ti(NMe(2))(2){NH(2)B(C(6)F(5))(3)} which was unsuccessful. Where Tp' = Tp and M = Ti and Zr and where Tp' = Tp* and M = Zr the complexes have been characterized by single crystal X-ray diffraction methods, revealing the first examples of octahedral amidoborane complexes of the group 4 metals. Attempts to drive the reactions to completion resulted in competing preferential hydrolysis of the amidoborane group, regenerating (C(6)F(5))(3)B·NH(3).

Treatment of Cp(2)HfCl(2) with two equivalents of LiNH(2)BH(C(6)F(5))(2) in toluene solution yields Cp(2)Hf{NHBH(C(6)F(5))(2)}, which has been crystallographically characterised. The otherwise base-free [NHBH(C(6)F(5))(2)] complex is stabilised by an agostic interaction.

The crystalline ion-pair [TiCl(NMe(2))(2)(NMe(2)H)(2)](+)[TiCl(2){NB(C(6)F(5))(3)}(NMe(2)H)(2)](-), in which the anion has a triply bonded nitridoborate ligand, is formed through the multiple activation of H(3)N x B(C(6)F(5))(3) when treated with [Ti(NMe(2))(3)Cl].

The ammonia adduct of tris(pentafluorophenyl)boron, (C6F5)3B.NH3, is a potentially tri-functional hydrogen-bond donor. Co-crystallisation with the bases acetonitrile, pyridine, tetrahydrofuran, tetramethylethylenediamine, 15-crown-5, 1,4-diazabicyclo[2.2.2]octane (DABCO), pyrazine and 4,4'-bipyridine results, not in donor exchange, but in the formation of supermolecules assembled through hydrogen bonding to second coordination sphere acceptors. The complexes have been characterised by elemental analysis, multinuclear NMR and single-crystal diffraction methods. The solid-state architectures range in complexity, from the hydrogen bonded pairing of (C6F5)3B.NH3, with a single monodentate acceptor molecule (e.g. MeCN to form (C6F5)3B.NH3.NCMe), through complexation with all three N-H groups to the macrocycle 15-crown-5, to the formation of infinite one-dimensional chains with pyrazine and DABCO, and to two-dimensional networks with the divergent acceptor 4,4'-bipyridine.

The crystalline ion-pair [TiCl(NMe2)2(NMe2H)2]+[TiCl2{NB(C6F5)3}(NMe2H)2]−, in which the anion has a triply bonded nitridoborate ligand, is formed through the multiple activation of H3N·B(C6F5)3 when treated with [Ti(NMe2)3Cl].

Summarization: Treatment of the ammonia adduct of tris(pentafluorophenyl)borane with 1.5 equivalents of pyrimidine affords a crystalline supramolecular complex. The solid state structure of the chloroform solvate has been determined by X-ray crystallography and is composed of two interpenetrating chiral (10,3)-a (srs) nets assembled through N–H⋯N hydrogen bonding interactions. Presented on: Inorganica Chimica Acta