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The reaction of [Rh 7 (CO) 16 ] 3- with BiCl 3 under N 2 and at room temperature results in the formation of the new heterometallic [Bi@Rh 12 (CO) 27 ] 3- cluster in high yields. Further controlled addition of BiCl 3 leads first to the formation of the dimeric [(Bi@Rh 12 (CO) 26 ) 2 Bi] 5- and the closo-[Bi@Rh 14 (CO) 27 Bi 2 ] 3- species in low yields, and finally, to the [Bi@Rh 17 (CO) 33 Bi 2 ] 4- cluster. All clusters were spectroscopically characterized by IR and electrospray ionization mass spectrometry, and their molecular structures were fully determined by X-ray diffraction studies. Notably, they represent the first examples of Bi atoms interstitially lodged in metallic cages that, in this specific case, are all based on an icosahedral geometry. Moreover, [Bi@Rh 14 (CO) 27 Bi 2 ] 3- forms an exceptional network of infinite zigzag chains in the solid state, thanks to intermolecular Bi-Bi distances.

Nanostructured titanium oxide difluoride embedded in a matrix of amorphous carbon was synthesized by pyrolysis of D-fructose in the presence of titanium tetrafluoride (optimal Ti/fructose molar ratio = 5.5), both in the solid state at ca. 150 °C and in suspension of 1,2-dichloroethane at reflux temperature. The resulting solid materials were characterized by powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), and elemental analysis. In every case, PXRD and TEM data indicated the presence of an unique crystalline phase (TiOF2) embedded in a light matrix (amorphous carbon). The average crystal size of the powder can be regulated by varying the reaction time.

Dinuclear complexes of formula Nb2Cl9[O2CCH(R)NR'R″2-κO,κO] (R = CH2CHMe2, R' = R″ = H, 1a; R = CH2Ph, R' = R″ = H, 1b; R = CH2CH2SCH3, R' = R″ = H, 1c; R = R' = H, R″ = Me, 1d; R = CH2Ph, R' = R″ = Me, 1e; Nb2Cl9[O2C⌈CH(CH2)3NH⌉], 1f) were prepared by allowing NbCl5 to react in dichloromethane with the appropriate α-amino acid in 1:2 amino acid/Nb molar ratio. The 1:1 reactions between MX5 (M = Nb, Ta; X = Cl, Br) and a series of α-amino acids resulted in the formation of the iminium salts [(R)CH═NR'R″2][MX6] (R = CH2Ph, R' = R″ = Me: M = Nb, X = Cl, 2a; M = Nb, X = Br, 2b; M = Ta, X = Cl, 2c; M = Ta, X = Br, 2d; R = CH2Ph, R' = R″ = H, M = Nb: X = Cl, 3a; X = Br, 3b; R = CH2CHMe2, R' = R″ = H, M = Nb, X = Cl, 4; R = R' = H, R″ = Me, M = Nb, X = Cl, 5). The formate/amino acidate derivative NbCl3(O2CH)[O2CCH(CH2Ph)NMe2], 6, was isolated and identified as coproduct of the 1:1 reaction between NbCl5 and N,N-dimethyl-l-phenylalanine, leading to 2a. All of the compounds were characterized by analytical and spectroscopic methods and by X-ray diffractometry in the cases of 2a, 2b, and 2d. Moreover, density functional theory studies were carried out to shed light on mechanistic and structural aspects.

Two new peraurated Ni-carbide carbonyl clusters have been prepared and structurally characterized, i.e. [Ni6(C)(CO)8(AuPPh3)8](2+) and [Ni12(C)(C2)(CO)17(AuPPh3)3](-). The latter is the first molecular cluster containing one carbide atom and one tightly bonded C2-unit. These display sub-van der Waals contacts suggesting the incipient formation of more extended C-C bonding.

The Co6C(CO)12(AuPPh3)4 carbide carbonyl cluster was obtained from the reaction of [Co6C(CO)15](2-) with Au(PPh3)Cl. This new species was investigated by variable-temperature (31)P NMR spectroscopy, X-ray crystallography, and density functional theory methods. Three different solvates were characterized in the solid state, namely, Co6C(CO)12(AuPPh3)4 (I), Co6C(CO)12(AuPPh3)4·THF (II), and Co6C(CO)12(AuPPh3)4·4THF (III), where THF = tetrahydrofuran. These are not merely different solvates of the same neutral cluster, but they contain three different isomers of Co6C(CO)12(AuPPh3)4. The three isomers I-III possess the same octahedral [Co6C(CO)12](4-) carbido-carbonyl core differently decorated by four [AuPPh3](+) fragments and showing a different Au(I)···Au(I) connectivity. Theoretical investigations suggest that the formation in the solid state of the three isomers during crystallization is governed by packing and van der Waals forces, as well as aurophilic and weak π-π and π-H interactions. In addition, the closely related cluster Co6C(CO)12(PPh3)(AuPPh3)2 was obtained from the reaction of [Co8C(CO)18](2-) with Au(PPh3)Cl, and two of its solvates were crystallographically characterized, namely, Co6C(CO)12(PPh3)(AuPPh3)2·toluene (IV) and Co6C(CO)12(PPh3)(AuPPh3)2·0.5toluene (V). A significant, even if minor, effect of the cocrystallized solvent molecules on the structure of the cluster was observed also in this case.

The 1 : 1 reaction of MoCl5 with 1,4-Me(SO3Me)C6H4 led to the isolation of crystalline Mo2O2Cl6[μ-κ(2)-1,4-Me(SO3Me)C6H4], 1, in low yields. Attempts to reproduce the synthesis of 1 from MoOCl3/1,4-Me(SO3Me)C6H4 resulted in the good-yield formation of [MoOCl2(μ-Cl)(κ(1)-1,4-Me(SO3Me)C6H4)]2, 2. The 1 : 1 reaction of MoCl5 with 1,4-Me(SO3H)C6H4·H2O selectively yielded Mo4O4Cl8[μ3-1,4-Me(SO3)C6H4]4, 3. Compounds 1 and 3 were characterized by X-ray diffractometry; moreover DFT calculations were carried out on 1-3 in order to shed light on their thermodynamic and structural features.

Metal hydrides are of fundamental importance in chemistry, both as solid-state materials and molecular compounds. The first low-valent molecular metal cluster containing an interstitial four-coordinate hydride in a tetrahedral site is decribed, which undergoes hydride migration from the surface to the tetrahedral cavity of the cluster upon coordination of a [AuPPh3 ](+) fragment. The [HFe4 (CO)12 (AuPPh3 )2 ](-) mono-anion, which contains a surface μ3 -H, was obtained from the reaction of [HFe4 (CO)12 ](3-) with two equivalents of [Au(PPh3 )Cl]. This is, in turn, transformed into the neutral [HFe4 (CO)12 (AuPPh3 )3 ] upon addition of a third [AuPPh3 ](+) fragment, with concomitant migration of the unique hydride from the surface of the cluster to its tetrahedral cavity. All of these species have been fully characterized in solution by means of IR and multinuclear NMR spectroscopy, and in the solid state by single-crystal X-ray diffractometry., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The new [{Co5C(CO)12}Au{Co(CO)4}](-), , cluster has been obtained from the reaction of [Co6C(CO)15](2-) with two equivalents of [AuCl4](-). reacts with an excess of HBF4 resulting in the formation of [{Co5C(CO)12}2Au](-), . The new derivatives [Co5C(CO)12(AuPPh3)], , and [Co5C(CO)11(AuPPh3)3], , have been obtained by reacting with two and four equivalents of [Au(PPh3)Cl], respectively. All the new species have been structurally characterised by means of X-ray crystallography as their [NEt4][], [NEt4][], [NMe3(CH2Ph)][], and thf·0.5C6H14 salts and solvates. may be viewed as a homoleptic Au(i) complex containing two [Co5C(CO)12](-) clusters as ligands. Similarly, and are heteroleptic Au(i) complexes containing one [Co5C(CO)12](-) cluster ligand as well as [Co(CO)4](-) or PPh3. Conversely, contains the [Co5C(CO)11](3-) cluster stabilized by three [AuPPh3](+) fragments. and have been investigated in solution by means of electrochemical and spectroelectrochemical methods, revealing a very rich redox propensity to form the closely related (n = 1-3) and (n = 0-3) species.

The oxidation and reduction reactions of [Co6C(CO)15](2-) have been studied in detail, leading to the isolation of several new Co-carbide carbonyl clusters. Thus, [Co6C(CO)15](2-) reacts in tetrahydrofuran (THF) with oxidants such as HBF4·Et2O and [Cp2Fe][PF6], resulting first in the formation of the previously reported [Co6C(CO)14](-); then, in CH2Cl2, the new dicarbide [Co11C2(CO)23](2-) is formed. The latter may be further oxidized, yielding the isostructural monoanion [Co11C2(CO)23](-), whereas its reduction with (cyclopentadienyl)2Co affords the unstable trianion [Co11C2(CO)23](3-), which decomposes during workup. Oxidation of [Co6C(CO)15](2-) in CH3CN with [C7H7][BF4] affords the same major products, and besides, the new monoacetylide [Co10(C2)(CO)21](2-) was obtained as side-product. Conversely, the reduction of [Co6C(CO)15](2-) in THF with increasing amounts of Na/naphthalene results in the following species: [Co6C(CO)13](2-), [Co11(C2)(CO)22](3-), [Co7C(CO)15](3-), [Co8C(CO)17](4-), [Co6C(CO)12](3-), and [Co(CO)4](-). The new [Co11C2(CO)23](-), [Co11C2(CO)23](2-), [Co10(C2)(CO)21](2-), [Co8C(CO)17](4-), [Co6C(CO)12](3-), and [Co7C(CO)15](3-) clusters were structurally characterized. Moreover, the paramagnetic species [Co11C2(CO)23](2-) and [Co6C(CO)12](3-) were investigated by means of electron paramagnetic resonance spectroscopy. Finally, electrochemical studies were performed on [Co11C2(CO)23](n-) (n = 1-3).

High yields of the ethoxo-α-aminoacidates of the general formula M(OEt)4[OC(O)CHRNHR'-κO,κN] (M = Nb, R = CH2Ph, R' = H, 2; R = CHMe2, R' = H, 3; R = CH2CHMe2, R' = H, 4; R = H, R' = Me, 5; R = CH2CH2SMe, R' = H, 6; M = Ta, R = CH2Ph, R' = H, 7; R = CH2CH2SMe, R' = H, 8) and M(OEt)4(OC(O)CH(CH2CH2CH2)NH-κO,κN) (M = Nb, 9; Ta, 10) have been obtained by the reaction of the l-enantiopure α-amino acid (or sarcosine) with a slight molar excess of M(OEt)5 (M = Nb, 1a; Ta, 1b) in a dichloromethane solution. The new complexes 2-10 have been fully characterized by spectroscopic and analytical methods and by X-ray diffraction for 2 and 7-9. Such X-ray structures are the first ones ever reported for niobium and tantalum coordination compounds containing an α-aminoacidato ligand. The early-late heterobimetallic derivative Ta(OEt)4[O2CCH(NH2)CH2CH2S(CH3)(AuCl)] (11) has been prepared by the reaction of 8 with a stoichiometric amount of Au(CO)Cl. The bulk polymerization of D,L-lactide initiated by complexes 2 and 7 gave a slightly heterotactic enchainment (Pr = 0.54 and 0.63, respectively), whereas complexes 1a and 1b formed fully atactic polylactide with P(r) ≈ 0.4.