Stereoselective addition reactions of diphenylphosphine to pyridyl and pyrimidylalkynes: Chiral 1,2-diheteroaryl-1,2-bis(diphenylphosphino)ethanes and their Group 6 metal carbonyl complexes

Bookham, Jonathan and Smithies, Darren M. (1999) Stereoselective addition reactions of diphenylphosphine to pyridyl and pyrimidylalkynes: Chiral 1,2-diheteroaryl-1,2-bis(diphenylphosphino)ethanes and their Group 6 metal carbonyl complexes. Journal of Organometallic Chemistry, 577 (2). pp. 305-315. ISSN 0022-328X

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Official URL: http://dx.doi.org/10.1016/S0022-328X(98)01078-X

Abstract

The base-catalysed addition of diphenylphosphine to the diarylethynes RCCR′ (R=R′=2-pyridyl 1; R=R′=3-pyridyl 2; R=2-pyridyl, R′=3-pyridyl 3; R=phenyl, R′=2-pyridyl 4, 3-pyridyl 5, 2-pyrimidyl 6) yield diphosphines of general formula Ph2PCH(R)CH(R′)PPh2 together with alkene by-products Ph2PC(R)=CHR′ and HC(R)=C(R′)PPh2 in all cases except 1. Selected P,P′-coordinated M(CO)4 complexes (M=Mo, W) of the diphosphines have been prepared and their 1H-, 13C- and 31P-NMR data are presented. The pattern of 13CO-NMR signals for the tetracarbonyl complexes was used unambiguously to determine the stereochemistry of the parent diphosphine. At moderately elevated temperatures, nitrogen coordination of 2-pyridyl and 2-pyrimidyl groups occurred for tetracarbonyl complexes of meso- or erythro-stereochemistry, but not for complexes of rac- or threo-form, to yield corresponding fac-tricarbonyl complexes. At 162°C the complex cis-rac-(CO)4W{P,P′-Ph2PCH(R)CH(R)PPh2} (R=R′=2-pyridyl) is converted quantitatively into fac-erythro-(CO)3W{P,P′,N-Ph2PCH(R)CH(R)PPh 2} via an inversion/N-coordination pathway.

Item Type: Article
Uncontrolled Keywords: carbonyl complexes, diphenylphosphine, group 6 metals, stereoselective addition
Subjects: F100 Chemistry
Department: Faculties > Health and Life Sciences > School of Life Sciences > Applied Sciences
Depositing User: Becky Skoyles
Date Deposited: 18 Feb 2015 10:00
Last Modified: 10 Aug 2015 11:52
URI: http://nrl.northumbria.ac.uk/id/eprint/18597

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