Reaction of metal chlorides (MCl2) with tripiperidinophosphine chalcogenides (Pip3PE) produces new dimer species (1)(2)(3)(4)(5)(6) of the formula [MCl2(Pip3PE)]2 (Pip = piperidinyl; E = S or Se; M = Hg, Cd or Zn). These coordination complexes were characterized by elemental analysis, IR, multinuclear ( 31 P, 113 Cd and 199 Hg) NMR spectroscopy and single crystal X-ray analysis. Compounds 1-6 exist as centrosymmetric homobimetallic dimers, [M(µ-Cl)Cl(Pip3PE)]2. Each dimer incorporates two µ2-chloro atoms and two terminal M-Cl bonds. The E atom of Pip3PE forms terminal M-E bonds {S; 2.305(11); Se: 2.412(6)-2.589(15) Å} and thus the geometry about each metal centre is distorted tetrahedral and the range of tetrahedral bond angles is 102.83(3) to 113.32(3) o . The P=Se bond lengths of 2.183(9)-2.205(2) Å in the selenide complexes are slightly elongated compared to those in the free ligands [2.1090(4) Å]. The results are discussed and compared with those obtained for related analogues.
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