Bis(iminophosphorano)methane derivatives as precursors of unusual ruthenium carbene complexes: A synthetic and DFT study
Bis(iminophosphorano)methane derivatives as precursors of unusual ruthenium carbene complexes: A synthetic and DFT study
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双（亚氨基膦）甲烷衍生物作为不寻常的钌卡宾配合物的前体：合成和DFT研究
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发表时间：
2004
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影响因子：
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通讯作者：
L. Veiros
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作者：
V. Cadierno;J. Díez;Joaquín García‐Álvarez;J. Gimeno;M. Calhorda;L. Veiros
The symmetric bis(iminophosphorano)methanes CH2[P{NP(O)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)) have been obtained by treatment of bis(diphenylphosphino)methane with a 2-fold excess of phosphorylated azides (RO)2P(O)N3. The asymmetric ligand CH2[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2] (2c) has been prepared by oxidation of Ph2PCH2P{NP(O)(OEt)2}Ph2 (1b) with (PhO)2P(O)N3. Compounds 2a−c can be deprotonated with sodium hydride, affording the corresponding methanide anions NaCH[P{NP(O)(OR)2}Ph2]2 (R = Ph (3a), Et (3b)) and NaCH[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2] (3c). Treatment of [{Ru(η6-p-cymene)(μ-Cl)Cl}2] with 3a−c results in the formation of the neutral complexes [RuCl(η6-p-cymene)(κ2(C,N)-CH[P{NP(O)(OR)2}Ph2]2)] (R = Ph (4a), Et (4b)) and [RuCl(η6-p-cymene)(κ2(C,N)-CH[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2])] (4c), via selective κ2(C,N) coordination of the bis(iminophosphorano)methanide anions to ruthenium. The cationic species [Ru(η6-p-cymene)(κ3(C,N,O)-CH[P{NP(O)(OR)2}Ph2]2)][SbF6] (R = Ph (5a), Et (5b)) an...
The symmetric bis(iminophosphorano)methanes CH2[P{NP(O)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)) have been obtained by treatment of bis(diphenylphosphino)methane with a 2-fold excess of phosphorylated azides (RO)2P(O)N3. The asymmetric ligand CH2[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2] (2c) has been prepared by oxidation of Ph2PCH2P{NP(O)(OEt)2}Ph2 (1b) with (PhO)2P(O)N3. Compounds 2a−c can be deprotonated with sodium hydride, affording the corresponding methanide anions NaCH[P{NP(O)(OR)2}Ph2]2 (R = Ph (3a), Et (3b)) and NaCH[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2] (3c). Treatment of [{Ru(η6-p-cymene)(μ-Cl)Cl}2] with 3a−c results in the formation of the neutral complexes [RuCl(η6-p-cymene)(κ2(C,N)-CH[P{NP(O)(OR)2}Ph2]2)] (R = Ph (4a), Et (4b)) and [RuCl(η6-p-cymene)(κ2(C,N)-CH[P{NP(O)(OPh)2}Ph2][P{NP(O)(OEt)2}Ph2])] (4c), via selective κ2(C,N) coordination of the bis(iminophosphorano)methanide anions to ruthenium. The cationic species [Ru(η6-p-cymene)(κ3(C,N,O)-CH[P{NP(O)(OR)2}Ph2]2)][SbF6] (R = Ph (5a), Et (5b)) an...