DFT computations reveal that cis-trans preferences in [PtX2(PR3)2] species are due to a combination of electrostatics, pi-backbonding, antisymbiosis, and solvation effects.

Nickel(II) complexes of ligands of the type Ar2PN(Me)PAr2 (Ar = ortho-substituted phenyl group) are highly active and poison-tolerant catalysts for the polymerization of ethylene.

The cage phosphines 1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane (1a) and 1,3,5,7-tetraethyl-6-phenyl-2,4,8,trioxa-6-phosphaadamantane (1b) have been made by the acid catalysed addition of PhPH(2) to the appropriate beta-diketones; the acid used (HCl, H(3)PO(4) or H(2)SO(4)) and its concentration affect the rate and selectivity of these condensation reactions. Phosphines 1a and 1b react with [PdCl(2)(NCPh)(2)] to form complexes trans-[PdCl(2)(1a)(2)](2a) and trans-[PdCl(2)(1b)(2)](2b) as mixtures of rac and meso diastereoisomers. The platinum(II) chemistry is more complicated and when 1a or 1b is added to [PtCl(2)(cod)], equilibrium mixtures of trans-[PtCl(2)L(2)] and [Pt(2)Cl(4)L(2)](L = or ) are formed in CH(2)Cl(2) solution. Meso/rac mixtures of trans-[MCl(CO)(1a)(2)] M = Ir (6a) or Rh (7a) are formed upon treatment of MCl(3).nH(2)O with an excess of 1a and the anionic cobalt complex [NHEt(3)][CoCl(3)(1a)](9) was isolated from the product formed by CoCl(2).6H(2)O and 1a. The nu(CO) values from the IR spectra of 6a and 7a suggest that 1a resembles a phosphonite in its bonding to Rh and Ir. Crystal structures of meso-2a, meso-2b, rac-6a and 9 are reported and in each case a small intracage C-P-C angle of ca. 94 degrees is observed; this may partly explain the bonding characteristics of ligands 1a and 1b. The cone angles for 1a and 1b are similar and large (ca. 200 degrees). Rhodium complexes of ligands 1a and 1b are hydroformylation catalysts with similarly high activity to catalysts derived from phosphites. The catalysts derived from 1a and 1b gave unusually low linear selectivity in the hydroformylation of hexenes. This feature has been further exploited in quaternary-selective hydroformylations of unsaturated esters; catalysts derived from 1a give better yields and regioselectivities than any previously reported catalyst.

The growing number of late-transition-metal olefin polymerization catalysts is almost exclusively based on "hard" nitrogen or oxygen donor ligands, 1 and despite the central role of diphosphine ligands in many other areas of homogeneous catalysis, "softer" phosphine donors generally yield very poor catalysts for this application. 2 We recently reported that the fourmembered nickel(II) chelates derived from the aminodiphosphines 1a-c (Figure 1) are very efficient catalysts for polymerization of ethylene, giving high-molecularweight linear polymer. 3 Here we show that ligands 1a-c are not unique, that other diphosphines give active polyethylene catalysts when suitably activated, and that catalytic activity and polymer structure are acutely sensitive to the nature of the ligand backbone and the substituents on the phosphorus. Nickel complexes of the bis(diarylphosphino)methane ligands 2a-d were activated and screened for polyethylene catalysis under the same conditions that

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