Structures of [Nb2Cl6(C4H8S)(PEt3)2], [Nb2Cl6(C4H8S)(C4H8O)2] and [Ta2Cl6(C4H8S)(PMe3)2]

Babaian-Kibala, Elizabeth; Cotton, F. Albert; Shang, Maoyu

doi:10.1107/s0108270191001555

Cited by 7 publications

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“…Such complexes are of interest for at least two reasons. First, there are several extant Nb(II) and Ta(II) face-sharing complexes of tetrahydrothiofuran (tht, C 4 H 8 S), − all of which are known to possess short and strong (nominally triple) M−M bonds. Second, a density functional theory (DFT) study by Ziegler and co-workers 9 has noted that substitution by thioethers of chloride bridges in Mo(III) dinuclear complexes leads to a considerable contraction in the Mo−Mo separation.…”

Section: Introductionmentioning

confidence: 99%

Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Petrie

Stranger

2003

Inorg. Chem.

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Density functional theory calculations have been used to investigate the structure and bonding of the d(3)d(3) bioctahedral complexes X(3)V(mu-S(CH(3))(2))(3)VX(3)(2)(-) (X = F(-), Cl(-), OH(-), SH(-), NH(2)(-)). According to geometry optimizations using the broken-symmetry approach and the VWN+B-LYP combination of density functionals, the halide-terminated complexes have a V-V bond order of approximately 2, while complexes featuring OH(-), SH(-), or NH(2)(-) as terminal ligands exhibit full triple bonding between the vanadium atoms. The tendency toward triple bonding in the latter complexes is consistent with an increased covalency of the vanadium-ligand bonds, and the influence of bond covalency is apparent also in the tendency for V-V bond elongation in the complexes with OH(-) and NH(2)(-) terminal ligands. Detailed examination of the composition of molecular orbitals in all of the thioether-bridged V(II) complexes substantiates the conclusion that the strong antiferromagnetic coupling which we have determined for these complexes (-J > 250 cm(-)(1)) is due to direct bonding between metal atoms rather than superexchange through the bridging ligands. As such, these V(II) complexes comprise the first apparent examples of multiple metal-metal bonding in first-transition-row, face-shared dinuclear complexes and are therefore of considerable structural and synthetic interest.

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Section: Introductionmentioning

confidence: 99%

Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Petrie

Stranger

2003

Inorg. Chem.

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“…For the synthesis of the principal reactant, see: Tsunoda & Hubert-Pfalzgraf (1982). For a related structure, see: Babaian-Kibala et al (1991).…”

Section: Related Literaturementioning

confidence: 99%

Di-μ-chlorido-μ-(dimethyl sulfide)-bis{dichlorido[(dimethyl selenide-κSe)(dimethyl sulfide-κS)(0.65/0.35)]niobium(III)}(Nb—Nb)

et al. 2012

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Key indicators: single-crystal X-ray study; T = 150 K; mean (S-C) = 0.003 Å; disorder in main residue; R factor = 0.023; wR factor = 0.057; data-to-parameter ratio = 26.1.The dinuclear compound, [Nb 2 Cl 6 (C 2 H 6 S) 1.7 (C 2 H 6 Se) 1 . The molecule lies on a twofold rotation axis that passes through the middle of this bond as well as through the bridging dimethyl sulfide ligand. The Nb III ion exists in an octahedral coordination environment defined by two terminal and two bridging Cl atoms, and (CH 3 ) 2 Se/(CH 3 ) 2 S ligands. The (bridging) ligand lying on the twofold rotation axis is an ordered (CH 3 ) 2 S ligand, whereas the terminal ones on a general position are a mixture of (CH 3 ) 2 Se and (CH 3 ) 2 S ligands in a 0.647 (2):0.353 (2) ratio (the methyl C atoms are also disordered). Related literature

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Niobium

KEE¹

1993

Coordination Chemistry Reviews

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Structures of [Nb2Cl6(C4H8S)(PEt3)2], [Nb2Cl6(C4H8S)(C4H8O)2] and [Ta2Cl6(C4H8S)(PMe3)2]

Cited by 7 publications

References 2 publications

Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Di-μ-chlorido-μ-(dimethyl sulfide)-bis{dichlorido[(dimethyl selenide-κSe)(dimethyl sulfide-κS)(0.65/0.35)]niobium(III)}(Nb—Nb)

Niobium

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Structures of [Nb2Cl6(C4H8S)(PEt3)2], [Nb2Cl6(C4H8S)(C4H8O)2] and [Ta2Cl6(C4H8S)(PMe3)2]

Cited by 7 publications

References 2 publications

Cl3V(μ-S(CH3)2)3VCl32-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Cl3V(μ-S(CH3)2)3VCl32-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Di-μ-chlorido-μ-(dimethyl sulfide)-bis{dichlorido[(dimethyl selenide-κSe)(dimethyl sulfide-κS)(0.65/0.35)]niobium(III)}(Nb—Nb)

Niobium

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Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding

Cl₃V(μ-S(CH₃)₂)₃VCl₃²^-: A First-Row, Face-Shared Bioctahedral Complex with Multiple Metal−Metal Bonding