The reaction of PdCl2, dppm and CS2 in CH(2)Cl(2)/MeOH results in the palladium carbodiphosphorane complex [Pd(Ph(2)PCH(2)Ph(2)PCPPh(2)CH(2)PPh(2)-P,C,P)Cl]Cl.

The first heterodimetallic PCP pincer complex, [PdAu(Cl)2(C(dppm)2)]Cl, was prepared from [PdCl(C(dppm)2)]Cl and [AuCl(tht)]. Both metals are attached to the carbon atom of the carbodiphosphorane (CDP) functionality and are connected via a very short d8−d10 pseudo-closed-shell interaction (Pd−Au = 2.8900(3) Å) which significantly modifies the ligand backbone conformation.

In a novel template synthesis of carbodiphosphoranes (CDPs), the phosphine functionalized CDP ligand C(dppm)(2) (dppm = Ph(2)PCH(2)PPh(2)) is formed in the coordination sphere of group 10 metals from CS(2) and 4 equivalents of dppm. The products are the PCP pincer complexes [M(Cl)(C(dppm)(2)-κ3P,C,P)]Cl (M = Ni, Pd, Pt) and 2 equivalents of dppmS. The compound C(dppm)(2), which is composed of a divalent carbon atom and two dppm subunits, represents a new PCP-type pincer ligand with the formally neutral carbon Lewis base of the CDP functionality as the central carbon. Treatment of [M(Cl)(C(dppm)(2)-κ3P,C,P)]Cl (M = Pd, Pt) with hydrochloric acid results in protonation at the CDP carbon atom and the formation of the PCP pincer complexes [M(Cl)(CH(dppm)(2)-κ3P,C,P)]Cl(2) (M = Pd, Pt). The PCP pincer ligand [CH(dppm)(2)](+) involves a formally cationic central carbon donor. The reaction of [Ni(Cl)(C(dppm)(2)-κ3P,C,P)]Cl with HCl leads to the extrusion of NiCl(2) and formation of the diprotonated CDP compound [CH(2)(dppm)(2)]Cl(2), from which the monoprotonated conjugate base [CH(dppm)(2)]Cl is obtained upon addition of bases, such as NH(3). The crystal structures of [M(Cl)(C(dppm)(2)-κ3P,C,P)]Cl (M = Ni, Pd, Pt), [Ni(Cl)(C(dppm)(2)-κ3P,C,P)](2)[NiCl(4)], [M(Cl)(CH(dppm)(2)-κ3P,C,P)]Cl(2) (M = Pd, Pt) as well as [CH(2)(dppm)(2)]Cl(2) and [CH(dppm)(2)]Cl are presented. A comparison of the solid state structures reveals interesting features, e.g. infinite supramolecular networks mediated by C-H···Cl hydrogen bond interactions and an unexpected loss of molecular symmetry upon protonation in the complexes [M(CH(dppm)(2)-κ3P,C,P)(Cl)]Cl(2) (M = Pd, Pt) as a result of the flexible ligand backbone. Additionally the new compounds were characterized comprehensively in solution by multinuclear (31)P, (13)C and (1)H NMR spectroscopy: Several spectroscopic parameters show a striking variability in particular regarding the carbodiphosphorane functionality. Furthermore the compound [Ni(Cl)(C(dppm)(2)-κ3P,C,P)]Cl was examined by cyclic voltammetry (CV) and could be shown to display quasi-reversible oxidative as well as reductive behaviour.

The reaction of the protonated PCP pincer carbodiphosphorane (CDP) complex [PdCl(CH(dppm)2)]Cl2 (1) with [PdCl2(MeCN)2] results in the opening of one ring of the pincer structure and affords the betaine [Pd2Cl5(CH(dppm)2)] (2). The [CH(dppm)2]+ ligand forms a five-membered chelate ring with the Pd(1)Cl2 moiety via the protonated CDP carbon (positively charged) and one phosphine functionality and bridges to the anionic Pd(2)Cl3 fragment via the second phosphine phosphorus. The complex is chiral due to a stereocenter at the protonated CDP carbon atom. Treatment of 2 with water effects deprotonation of the CDP carbon, C–H activation at one methylene group, and the coordination of the second Pd to the CDP carbon. The resulting tricyclic complex [Pd2Cl3(C(dppm)(Ph2CHPh2))] (3) is the first compound with two Pd centers coordinated to a CDP carbon. Compound 3 forms a single-stranded helicate structure and exhibits two interdependent carbon stereocenters, resulting in only two possible enantiomers. The complexes 2·2CH2Cl2 and 3·3CH2Cl2 crystallize in the chiral space group P21, whereby a spontaneous resolution of the enantiomers occurs in both cases.

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