Stability in Solution of (Chloromethyl)palladium(II) Complexes: X-ray Structures of trans-Bis(triphenylphosphine)chloro(chloromethyl)palladium(II) and -platinum(II) and Comparison of the Relative Stabilities of Analogous Palladium and Platinum Chloromethyl Complexes Containing Phosphine Ligands

cis-Dichloro(dimethylaminomethylene)(triphenylphosphine)palladium(II) acetone solvate

“…The interatomic distances in (I) are very similar to those reported (Bare®eld et al, 1982) for (II), except that the MÐP bond length is somewhat greater for M = Pd [2.2495 (7) A Ê ] than for M = Pt [2.220 (2) A Ê ]. Similar differences have been found for other pairs of Pd and Pt complexes containing phosphine ligands (McCrindle et al, 1995). The Pd1ÐC1 [1.948 (2) A Ê ] and C1ÐN1 [1.274 (3) A Ê ] bonds are relatively short, consistent with %-bonding within the metal±carbene moiety comparable with those observed in other Pd±carbene complexes (Dixon & Dixon, 1995).…”

Gold Carbene or Carbenoid: Is There a Difference?

“…[ 45 ] Thus, [(Ph 3 P) 2 M(CH 2 Cl)Cl] (M=Pd, Pt) are two well-characterized examples of d 8 square planar Group 11 metal carbenoids. [ 46 ] Indeed, two authentic gold(I) carbenoids have been prepared and structurally characterized. [ 47 ] As expected, the metal–carbon bond length in these gold(I) carbenoids (2.09 Å) is longer than in gold(I) carbenes of Table 1 .…”

“…More general, and didactically useful, is the distinction between carbenoids and carbenes as different species that are, however, related by the addition/elimination of an X − group, regardless of the double bond character of the metal–carbon bond in the carbene (Scheme ) 45. Thus, [(Ph 3 P) 2 M(CH 2 Cl)Cl] (M=Pd, Pt) are two well‐characterized examples of d 8 square planar Group 11 metal carbenoids 46. Indeed, two authentic gold(I) carbenoids have been prepared and structurally characterized 47.…”

Reaction of a Rhodium(III) α-Chlorotolyl Complex with Water and Oxygen: Stable Rhodium Peroxo Compounds

“…In this context it is interesting to mention a study on the stability of a series of chloro(chloromethyl)palladium(II) complexes in CDCl 3 solution both in the absence and presence of air published by McCrindle et al . Depending on the nature of the ligands it was found that the chloromethyl moiety could react in three ways: (i) to formaldehyde by oxidation; (ii) to ylide complexes by reaction with a sulfide ligand; (iii) coupling to ethene by reaction of two chloromethyl complexes to give ethene and chloropalladium complexes or to propene by reaction of ethene with a (chloromethyl)palladium to give chloropalladium complexes.…”