Abstract
The symmetrical diphosphanes R2P-PR2 {where R=Ph (1a), Cy (1b), or But (1c)} are made by the reaction of R2PLi with R2PCl. The unsymmetrical diphosphanes R2P-PR'(2) {where R=Bu-t and R'=Ph (2a); R = Bu-t and R' =o-Tol ( 2b); R=Cy and R'= Ph ( 2c); R=Cy and R' =o- Tol ( 2d); R=Cy and R'=Bu-t ( 2e)} are made by the reaction of R2P( BH3) Li with R'2PCl followed by deprotection with Et2NH. Diphosphanes 1a, b and 2a-d react with ZCtCZ ( Z=CO2Me) to give the corresponding R-2-PCZ=CZPR(2) (3a, b) or R(2)PCZ=CZPR'(2) (4a-d). The reaction of 2a, b with HC=CZ give the corresponding R2PCH=CZPR(2) ( 5a, b). A mechanism is proposed that accounts for the cis stereospecificity and the regioselectivity of these diphosphinations. Treatment of [PtCl2(1,5-cod)] or [PdCl2(NCPh)(2)] with a selection of the diphosphines (3-5) gave the expected chelate complexes, four of which, [PtCl2(3b)], [PtCl2(4a)], [PtCl2(4c)], and [PdCl2(4a)], have had their crystal structures determined.
Original language | English |
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Pages (from-to) | 5937-5945 |
Number of pages | 9 |
Journal | Organometallics |
Volume | 25 |
Issue number | 25 |
DOIs | |
Publication status | Published - 4 Dec 2006 |
Bibliographical note
Publisher: American Chemical SocietyOther identifier: IDS 109HT