Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9 (X = C or As) and MZB10 cages (Z = S, Se or Te)

Donnacha O'Connell; Jennifer C. Patterson; Trevor R. Spalding; George Ferguson; John F. Gallagher; Yiwei Li; John D. Kennedy; Ramón Macías; Mark Thornton-Pett; Josef Holub

doi:10.1039/DT9960003323

Conformational polymorphism and fluxional behaviour of M(PR₃)₂ units in closo-twelve-atom metallaheteroboranes with MX₂B₉ (X = C or As) and MZB₁₀ cages (Z = S, Se or Te)

Donnacha O'Connell
, Jennifer C. Patterson
, Trevor R. Spalding
, George Ferguson
, John F. Gallagher
, Yiwei Li
, John D. Kennedy
, Ramón Macías
, Mark Thornton-Pett
, Josef Holub

School of Chemistry

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

Abstract

The compounds [3,3-(PEt₃)₂-closo-3,1,2-PtAs₂B ₉H₉] 1 and [2,2-(PMe₂Ph)₂-closo-2,1-PtSB₁₀H₁₀] 2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt₃)₂ unit above the As₂B₃ face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe₂Ph)₂ unit above the SB₁₀ cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C₂B₉H₁₁, As₂B₉H₉, SeB₁₀H₁₀ and TeB₁₀H₁₀ ligands. A mechanism for the rotation of M(PR₃)₂ units above heteroborane ligand faces is suggested. It involves shifting the M(PR₃)₂ unit via ηⁿ-bonded species (n < 5) with a concomitant twisting of the M(PR₃)₂ unit about an axis passing approximately through the metal atom and the antipodal B atom.

Original language	English
Pages (from-to)	3323-3333
Number of pages	11
Journal	Journal of the Chemical Society. Dalton Transactions
Issue number	15
DOIs	https://doi.org/10.1039/DT9960003323
Publication status	Published - 7 Aug 1996

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O'Connell, D., Patterson, J. C., Spalding, T. R., Ferguson, G., Gallagher, J. F., Li, Y., Kennedy, J. D., Macías, R., Thornton-Pett, M., & Holub, J. (1996). Conformational polymorphism and fluxional behaviour of M(PR₃)₂ units in closo-twelve-atom metallaheteroboranes with MX₂B₉ (X = C or As) and MZB₁₀ cages (Z = S, Se or Te). Journal of the Chemical Society. Dalton Transactions, (15), 3323-3333. https://doi.org/10.1039/DT9960003323

@article{e2c0abd778f44fa5af352bb4dcfa088a,

title = "Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9 (X = C or As) and MZB10 cages (Z = S, Se or Te)",

abstract = "The compounds [3,3-(PEt3)2-closo-3,1,2-PtAs2B 9H9] 1 and [2,2-(PMe2Ph)2-closo-2,1-PtSB10H10] 2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt3)2 unit above the As2B3 face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe2Ph)2 unit above the SB10 cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C2B9H11, As2B9H9, SeB10H10 and TeB10H10 ligands. A mechanism for the rotation of M(PR3)2 units above heteroborane ligand faces is suggested. It involves shifting the M(PR3)2 unit via ηn-bonded species (n < 5) with a concomitant twisting of the M(PR3)2 unit about an axis passing approximately through the metal atom and the antipodal B atom.",

author = "Donnacha O'Connell and Patterson, \{Jennifer C.\} and Spalding, \{Trevor R.\} and George Ferguson and Gallagher, \{John F.\} and Yiwei Li and Kennedy, \{John D.\} and Ram{\'o}n Mac{\'i}as and Mark Thornton-Pett and Josef Holub",

year = "1996",

month = aug,

day = "7",

doi = "10.1039/DT9960003323",

language = "English",

pages = "3323--3333",

journal = "Journal of the Chemical Society. Dalton Transactions",

issn = "1470-479X",

publisher = "Royal Society of Chemistry",

number = "15",

}

O'Connell, D, Patterson, JC, Spalding, TR, Ferguson, G, Gallagher, JF, Li, Y, Kennedy, JD, Macías, R, Thornton-Pett, M & Holub, J 1996, 'Conformational polymorphism and fluxional behaviour of M(PR₃)₂ units in closo-twelve-atom metallaheteroboranes with MX₂B₉ (X = C or As) and MZB₁₀ cages (Z = S, Se or Te)', Journal of the Chemical Society. Dalton Transactions, no. 15, pp. 3323-3333. https://doi.org/10.1039/DT9960003323

Conformational polymorphism and fluxional behaviour of M(PR₃)₂ units in closo-twelve-atom metallaheteroboranes with MX₂B₉ (X = C or As) and MZB₁₀ cages (Z = S, Se or Te). / O'Connell, Donnacha; Patterson, Jennifer C.; Spalding, Trevor R. et al.
In: Journal of the Chemical Society. Dalton Transactions, No. 15, 07.08.1996, p. 3323-3333.

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

TY - JOUR

T1 - Conformational polymorphism and fluxional behaviour of M(PR3)2 units in closo-twelve-atom metallaheteroboranes with MX2B9 (X = C or As) and MZB10 cages (Z = S, Se or Te)

AU - O'Connell, Donnacha

AU - Patterson, Jennifer C.

AU - Spalding, Trevor R.

AU - Ferguson, George

AU - Gallagher, John F.

AU - Li, Yiwei

AU - Kennedy, John D.

AU - Macías, Ramón

AU - Thornton-Pett, Mark

AU - Holub, Josef

PY - 1996/8/7

Y1 - 1996/8/7

N2 - The compounds [3,3-(PEt3)2-closo-3,1,2-PtAs2B 9H9] 1 and [2,2-(PMe2Ph)2-closo-2,1-PtSB10H10] 2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt3)2 unit above the As2B3 face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe2Ph)2 unit above the SB10 cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C2B9H11, As2B9H9, SeB10H10 and TeB10H10 ligands. A mechanism for the rotation of M(PR3)2 units above heteroborane ligand faces is suggested. It involves shifting the M(PR3)2 unit via ηn-bonded species (n < 5) with a concomitant twisting of the M(PR3)2 unit about an axis passing approximately through the metal atom and the antipodal B atom.

AB - The compounds [3,3-(PEt3)2-closo-3,1,2-PtAs2B 9H9] 1 and [2,2-(PMe2Ph)2-closo-2,1-PtSB10H10] 2 were synthesised and characterised by NMR spectroscopy and X-ray crystallography. Crystals of 1 exhibit conformational polymorphism with five conformers of the Pt(PEt3)2 unit above the As2B3 face; those of 2 contain single conformers. The free energy of the barrier to rotation of the Pt(PMe2Ph)2 unit above the SB10 cage ligand in 2 has been determined in chloroform solution and is compared with data from other platinum and palladium metallaheteroboranes containing C2B9H11, As2B9H9, SeB10H10 and TeB10H10 ligands. A mechanism for the rotation of M(PR3)2 units above heteroborane ligand faces is suggested. It involves shifting the M(PR3)2 unit via ηn-bonded species (n < 5) with a concomitant twisting of the M(PR3)2 unit about an axis passing approximately through the metal atom and the antipodal B atom.

UR - https://www.scopus.com/pages/publications/33748513443

U2 - 10.1039/DT9960003323

DO - 10.1039/DT9960003323

M3 - Article

AN - SCOPUS:33748513443

SN - 1470-479X

SP - 3323

EP - 3333

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 15

ER -

Conformational polymorphism and fluxional behaviour of M(PR₃)₂ units in closo-twelve-atom metallaheteroboranes with MX₂B₉ (X = C or As) and MZB₁₀ cages (Z = S, Se or Te)

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