Journal of the Chemical Society, Dalton Transactions p. 3323 - 3333 (1996)
Update date:2022-08-03
Topics:
O'Connell, Donnacha
Patterson, Jennifer C.
Spalding, Trevor R.
Ferguson, George
Gallagher, John F.
Li, Yiwei
Kennedy, John D.
Macias, Ramon
Thornton-Pett, Mark
Holub, Josef
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.
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