title: Reactivity of Germylene toward Phosphorus-Containing Compounds: Nucleophilic Addition and Tautomerism.
abstract: A series of phosphorus-substituted germanium(II) complexes, L(1)GeR [L(1) = CH{(CMe)(2,6-(i)Pr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (O(n)Bu)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 L(1)GeOPPh2 (4) rather than the expected isomeric product L(1)GeP(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.
authors.forename: Yile
authors.initials: Y
authors.lastname: Wu
authors.forename: Liu Leo
authors.initials: LL
authors.lastname: Liu
authors.forename: Jue
authors.initials: J
authors.lastname: Su
authors.forename: Kaili
authors.initials: K
authors.lastname: Yan
authors.forename: Tao
authors.initials: T
authors.lastname: Wang
authors.forename: Jun
authors.initials: J
authors.lastname: Zhu
authors.affiliation: §School of Pharmaceutical Sciences, Xiamen University, Xiamen 361102, Fujian, China.
authors.forename: Xiang
authors.initials: X
authors.lastname: Gao
authors.forename: Yuxing
authors.initials: Y
authors.lastname: Gao
authors.forename: Yufen
authors.initials: Y
authors.lastname: Zhao
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D005857:Germanium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D063086:Organothiophosphates / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D056831:Coordination Complexes; D063086:Organothiophosphates; D005857:Germanium; D010758:Phosphorus