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Allenyl-propargyl tautomerism at palladium(IV) and platinum(IV) centres


Canty, AJ and Jin, H and Penny, JD, Allenyl-propargyl tautomerism at palladium(IV) and platinum(IV) centres, Journal of Organometallic Chemistry, 573, (1-2) pp. 30-35. ISSN 0022-328X (1999) [Refereed Article]

DOI: doi:10.1016/S0022-328X(98)00598-1


The propargylic bromides MeCCCH 2Br and HCCCH 2Br undergo oxidative addition reactions with [MMe 2{(pz) 3BH}] - {M=Pd, Pt; [(pz) 3BH] -=tris(pyrazol-1-yl)borate}, [Pd(CH 2CH 2CH 2CH 2){(pz) 3BH}] - and MMe 2(bpy) (M=Pd, Pt; bpy=2,2′-bipyridine) to form the octahedral metal(IV) complexes MMe 2(CH 2CCMe){(pz) 3BH} [M=Pd (1), Pt (3)], Pd(CH 2CH 2CH 2CH 2)(CH 2CCMe){(pz) 3BH} (2), Pd(CH 2CH 2CH 2CH 2)(CH=C=CH 2){(pz) 3BH} (5), PdMe 2(CH=C=CH 2){(pz) 3BH} (4), a mixture of tautomers PtMe 2(CH 2CCH){(pz) 3BH} (6a) and PtMe 2(CH=C=CH 2){(pz) 3BH} (6b), MBrMe 2(CH 2CCMe)(bpy) [M=Pd (7), Pt (8)], a mixture of structural isomers PdBrMe 2(CH 2CCH)(bpy) with the propargyl group trans to bromine (9a) and bpy (9b), and a mixture of tautomers and structural isomers for PtBrMe 2(CH 2CCH)(bpy) (10a, 10b) and PtBrMe 2(CH=C=CH 2)(bpy) (10c, 10d). The preference for adoption of the propargyl or allenyl form is dependent upon metal, ancillary ligands, and substitution in the propargyl/allenyl fragment M-C 3H 3 and M-C 3H 2Me: for M-C 3H 2Me propargyl is favoured and for M-C 3H 3 allenyl is favoured for the Pd(IV)/[(pz) 3BH] - substrates but propargyl is favoured for the Pd(IV)/bpy substrate.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Jin, H (Dr Hong Jin)
UTAS Author:Penny, JD (Mr Justin David Penny)
ID Code:16414
Year Published:1999
Web of Science® Times Cited:22
Deposited By:Chemistry
Deposited On:1999-08-01
Last Modified:2011-08-04

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