Issue 10, 1999

Phosphine exchange reactions involving cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the oxidative addition of 1,2-B2Cl2(NMe2)2 to Pt0

Abstract

The reaction between the platinum(II) bis(boryl) complex cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the tertiary phosphines PMe3, PEt3, PMe2Ph, PMePh2 and dcpe [1,2-bis(dicyclohexylphosphino)ethane] and the phosphite P(OEt)3 afforded the new complexes cis-[Pt(PR3)2(Bcat)2] (PR3 = PMe3, PEt3, PMe2Ph or PMePh2), cis-[Pt(dcpe)(Bcat)2] and cis-[Pt{P(OEt)3}2(Bcat)2]. With PCy3 the mixed phosphine species cis-[Pt(PCy3)(PPh3)(Bcat)2] is the major product and was characterised by X-ray crystallography. With P(OMe)3 reductive elimination of B2(cat)2 and the formation of platinum(>0>) products occurs exclusively whereas with dmpe [1,2-bis(dimethylphosphino)ethane] the only identifiable product is the platinum(II) species [Pt(dmpe)2]Cl2. With dppm [bis(diphenylphosphino)methane] a reaction occurs to give a product assigned the structure cis-[Pt(dppm)(Bcat)2] or [Pt2(dppm)2(Bcat)4] but two binuclear products were isolated as minor products, namely [Pt2(PPh3)(µ-dppm)2(Bcat)(µ-Bcat)] and [Pt21-dppm)(µ-dppm)2(Bcat)(µ-Bcat)]. Both compounds were characterised by X-ray crystallography and shown to contain unusual semi-bridging Bcat groups. The reaction between [Pt(PPh3)2(η-C2H4)] and the diborane(4) compound 1,2-B2Cl2(NMe2)2 is also described which results in B–B bond oxidative addition yielding cis-[Pt(PPh3)2{BCl(NMe2)}2] and a complex to which this bis(boryl) subsequently rearranges, namely trans-[PtCl(PPh3)2{BCl(NMe2)}]. Both of these complexes were characterised by X-ray crystallography and have geometries typical of cis-bis(boryl) and trans-boryl chloride complexes respectively.

Supplementary files

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1999, 1687-1694

Phosphine exchange reactions involving cis-[Pt(PPh3)2(Bcat)2] (cat = 1,2-O2C6H4) and the oxidative addition of 1,2-B2Cl2(NMe2)2 to Pt0

D. Curtis, M. J. Gerald Lesley, N. C. Norman, A. Guy Orpen and J. Starbuck, J. Chem. Soc., Dalton Trans., 1999, 1687 DOI: 10.1039/A810006C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements