Synthesis and Structure of a Tetrameric Tantalum(III) Compound

P. F. Gilletti; V. G. Young; T. M. Brown

doi:10.1021/ic00320a019

Synthesis and Structure of a Tetrameric Tantalum(III) Compound

P. F. Gilletti, V. G. Young, T. M. Brown

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

12 Scopus citations

Abstract

The tetrameric compound [Ta2Cl4 (μ-Cl)₂(μ-SC₄H₈)]₂(μ-Ph₂PCH₂CH₂PPh₂)2.2C₇H₈ has been prepared from the reaction of Ta₂Cl₄(SC4H₈)2 (μ-Cl)2 (μ-SC₄H₈) (1) with Ph₂PCH₂CH₂PPh₂(dppe). The compound crystallizes in the space group Bbcm, which is the bca setting of space group No. 64, Cmca. The cell parameters are a = 12.706 (6) A, b = 27.240 (7) A, c = 25.93 (2) A, V = 8976 (9) A³, and Z= 4. The structure consists of two confacial bioctahedral units of Ta₂Cl₄(μ-Cl)₂(μ-SC₄H₈) bridged by two Ph₂PCH₂CH2PPh₂ ligands. The Ta=Ta double-bond distance within the bioctahedral units is 2.704 (2) A with no metal-metal bonding between the separate dimeric units of the tetramer. To our knowledge this compound is the first tetrameric tantalum(III) compound reported in the literature. It is a deviation from the products previously reported for the reactions of analogous niobium or tantalum dimeric compounds with bidentate phosphine ligands, all of which result in the formation of edge-shared dimeric compounds of the type M₂C1₆(PP)₂(where PP = bidentate phosphine ligand). The fact that the bridging (SC₄H₈) ligand is not substituted in the tantalum tetramer suggests that the ligand is less labile in 1 than in its niobium analogue.

Original language	English (US)
Pages (from-to)	4034-4036
Number of pages	3
Journal	Inorganic Chemistry
Volume	28
Issue number	21
DOIs	https://doi.org/10.1021/ic00320a019
State	Published - Oct 1 1989

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@article{20e476cd5919461090b64c0fa71ab8ed,

title = "Synthesis and Structure of a Tetrameric Tantalum(III) Compound",

abstract = "The tetrameric compound [Ta2Cl4 (μ-Cl)2(μ-SC4H8)]2(μ-Ph2PCH2CH2PPh2)2.2C7H8 has been prepared from the reaction of Ta2Cl4(SC4H8)2 (μ-Cl)2 (μ-SC4H8) (1) with Ph2PCH2CH2PPh2(dppe). The compound crystallizes in the space group Bbcm, which is the bca setting of space group No. 64, Cmca. The cell parameters are a = 12.706 (6) A, b = 27.240 (7) A, c = 25.93 (2) A, V = 8976 (9) A3, and Z= 4. The structure consists of two confacial bioctahedral units of Ta2Cl4(μ-Cl)2(μ-SC4H8) bridged by two Ph2PCH2CH2PPh2 ligands. The Ta=Ta double-bond distance within the bioctahedral units is 2.704 (2) A with no metal-metal bonding between the separate dimeric units of the tetramer. To our knowledge this compound is the first tetrameric tantalum(III) compound reported in the literature. It is a deviation from the products previously reported for the reactions of analogous niobium or tantalum dimeric compounds with bidentate phosphine ligands, all of which result in the formation of edge-shared dimeric compounds of the type M2C16(PP)2(where PP = bidentate phosphine ligand). The fact that the bridging (SC4H8) ligand is not substituted in the tantalum tetramer suggests that the ligand is less labile in 1 than in its niobium analogue.",

author = "Gilletti, {P. F.} and Young, {V. G.} and Brown, {T. M.}",

year = "1989",

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T1 - Synthesis and Structure of a Tetrameric Tantalum(III) Compound

AU - Gilletti, P. F.

AU - Young, V. G.

AU - Brown, T. M.

PY - 1989/10/1

Y1 - 1989/10/1

N2 - The tetrameric compound [Ta2Cl4 (μ-Cl)2(μ-SC4H8)]2(μ-Ph2PCH2CH2PPh2)2.2C7H8 has been prepared from the reaction of Ta2Cl4(SC4H8)2 (μ-Cl)2 (μ-SC4H8) (1) with Ph2PCH2CH2PPh2(dppe). The compound crystallizes in the space group Bbcm, which is the bca setting of space group No. 64, Cmca. The cell parameters are a = 12.706 (6) A, b = 27.240 (7) A, c = 25.93 (2) A, V = 8976 (9) A3, and Z= 4. The structure consists of two confacial bioctahedral units of Ta2Cl4(μ-Cl)2(μ-SC4H8) bridged by two Ph2PCH2CH2PPh2 ligands. The Ta=Ta double-bond distance within the bioctahedral units is 2.704 (2) A with no metal-metal bonding between the separate dimeric units of the tetramer. To our knowledge this compound is the first tetrameric tantalum(III) compound reported in the literature. It is a deviation from the products previously reported for the reactions of analogous niobium or tantalum dimeric compounds with bidentate phosphine ligands, all of which result in the formation of edge-shared dimeric compounds of the type M2C16(PP)2(where PP = bidentate phosphine ligand). The fact that the bridging (SC4H8) ligand is not substituted in the tantalum tetramer suggests that the ligand is less labile in 1 than in its niobium analogue.

AB - The tetrameric compound [Ta2Cl4 (μ-Cl)2(μ-SC4H8)]2(μ-Ph2PCH2CH2PPh2)2.2C7H8 has been prepared from the reaction of Ta2Cl4(SC4H8)2 (μ-Cl)2 (μ-SC4H8) (1) with Ph2PCH2CH2PPh2(dppe). The compound crystallizes in the space group Bbcm, which is the bca setting of space group No. 64, Cmca. The cell parameters are a = 12.706 (6) A, b = 27.240 (7) A, c = 25.93 (2) A, V = 8976 (9) A3, and Z= 4. The structure consists of two confacial bioctahedral units of Ta2Cl4(μ-Cl)2(μ-SC4H8) bridged by two Ph2PCH2CH2PPh2 ligands. The Ta=Ta double-bond distance within the bioctahedral units is 2.704 (2) A with no metal-metal bonding between the separate dimeric units of the tetramer. To our knowledge this compound is the first tetrameric tantalum(III) compound reported in the literature. It is a deviation from the products previously reported for the reactions of analogous niobium or tantalum dimeric compounds with bidentate phosphine ligands, all of which result in the formation of edge-shared dimeric compounds of the type M2C16(PP)2(where PP = bidentate phosphine ligand). The fact that the bridging (SC4H8) ligand is not substituted in the tantalum tetramer suggests that the ligand is less labile in 1 than in its niobium analogue.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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ER -

Synthesis and Structure of a Tetrameric Tantalum(III) Compound

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