Reactivity of Germylene toward Phosphorus-Containing Compounds: Nucleophilic Addition and Tautomerism

A series of phosphorus-substituted germanium(II) complexes, L1GeR [L1 = CH{(CMe)(2,6-iPr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (OnBu)2; 6a, R = OP(S)Ph2; 6b, R = OP(S)(OEt)2], were synthesized
through the direct activation of various organic phosphorus compounds
by N-heterocyclic ylide-like germylene 1. These compounds
were characterized by IR and NMR spectroscopy, and 4, 5a, 6a, and 6b were further investigated
by X-ray crystallography. Interestingly, the reaction of 1 with Ph2P(O)H produced the tricoordinated phosphorus(III)
species L1GeOPPh2 (4) rather than
the expected isomeric product L1GeP(O)Ph2. The
reaction of 1 with dialkylthiophosphoric acid and diphenylthiophosphinic
acid resulted in the products 6a and 6b containing
the PS double bond rather than the PO double bond.