Home
Resources
Publications
Steric Versus Electronic Factors in Metallacarborane Isomerisation: Nickelacarboranes With 3,1,2-, 4,1,2- And 2,1,8-NiC2B9 Architectures and Pendant Carborane Groups, Derived From 1,1'-bis(o-carborane)

Steric Versus Electronic Factors in Metallacarborane Isomerisation: Nickelacarboranes With 3,1,2-, 4,1,2- And 2,1,8-NiC2B9 Architectures and Pendant Carborane Groups, Derived From 1,1'-bis(o-carborane)

Dipendu Mandal, Wing Y Man, Georgina M Rosair, Alan J Welch

Dalton Trans. 2016 Oct 14;45(38):15013-25.

PMID: 27560357

Abstract:

Metalation of the [7-(1'-1',2'-closo-C2B10H11)-7,8-nido-C2B9H10](2-) dianion with various {NiPP(2+)} or {NiP2(2+)} fragments (PP = chelating diphosphine; P = monodentate phosphine or phosphite) leads either to unisomerised 3,1,2-NiC2B9 species or to isomerised 4,1,2-NiC2B9 or 2,1,8-NiC2B9 species, all with a pendant C2B10 substituent. The products [1-(1'-1',2'-closo-C2B10H11)-3-dppe-3,1,2-closo-NiC2B9H10] (1), [2-(1'-1',2'-closo-C2B10H11)-4-dppe-4,1,2-closo-NiC2B9H10] (2), [8-(1'-1',2'-closo-C2B10H11)-2-dmpe-2,1,8-closo-NiC2B9H10] (3), [1-(1'-1',2'-closo-C2B10H11)-3,3-(PMe3)2-3,1,2-closo-NiC2B9H10] (4), [1-(1'-1',2'-closo-C2B10H11)-3,3-(PMe2Ph)2-3,1,2-closo-NiC2B9H10] (6), [1-(1'-1',2'-closo-C2B10H11)-3,3-{P(OMe)3}2-3,1,2-closo-NiC2B9H10] (9) and [1-(1'-1',2'-closo-C2B10H11)-2,2-{P(OMe)3}2-2,1,8-closo-NiC2B9H10] (10) were fully characterised spectroscopically and crystallographically, whilst [2-(1'-1',2'-closo-C2B10H11)-4,4-(PMePh2)2-4,1,2-closo-NiC2B9H10] (8) was characterised spectroscopically. Overall the results suggest that an important factor in a 3,1,2 to 4,1,2 isomerisation is the relief gained from steric crowding, whereas a 3,1,2 to 2,1,8 isomerisation appears to be favoured by strongly electron-donating ligands on the metal.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP219628010	2,5-Didodecyl-1,4-di-1-propynylbenzene		219628-01-0	Price
IAR4247380	1,3-Dilinoleoyl-rac-glycerol			Price

As a specialist in analytical chemical Products, Alfa Chemistry offers consumers a wealth of raw materials and a full range of technologies and services.

QUICK LINKS

HEADQUARTERS

Tel:

Fax:

Email: