MECHANISM OF THERMAL-DECOMPOSITION OF TRANS-DIETHYLBIS(TERTIARY PHOSPHINE)PALLADIUM(II) - STERIC EFFECTS OF TERTIARY PHOSPHINE-LIGANDS ON THE STABILITY OF DIETHYLPALLADIUM COMPLEXES
MECHANISM OF THERMAL-DECOMPOSITION OF TRANS-DIETHYLBIS(TERTIARY PHOSPHINE)PALLADIUM(II) - STERIC EFFECTS OF TERTIARY PHOSPHINE-LIGANDS ON THE STABILITY OF DIETHYLPALLADIUM COMPLEXES
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DOI：
10.1021/ja00541a013
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
YAMAMOTO, A
中科院分区：
文献类型：
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作者：
OZAWA, F;ITO, T;YAMAMOTO, A
反式-[Pdr‘2(PR3)2]具有不同空间体积的烷基和叔膦配体(R’=Et，Pr3=PMe2Ph(1)，PEt3(2)，PEt2Ph(3)，PMePh2(4)，PEtPh2(5)；R‘=Pr(6)，Bu(7)，Pr3=PMe2Ph)在溶液中按1：1的比例通过^消除过程进行热分解。对反式-[PdEt2(Pr3)2]的热分解动力学研究表明，它们的热分解服从钯配合物浓度的一级反应规律。热分解主要来自四配位的络合物，而不解离叔膦配体。磷化氢的加入完全阻断了涉及磷化氢解离的次要平行热分解途径。具有不同空间体积的乙基钯配合物的热分解活化能为
trans-[PdR'2 (PR3) 2] with a series of alkyl groups and tertiary phosphine ligands of various steric bulkiness (R'= Et, PR3= PMe2Ph (1), PEt3 (2), PEt2Ph (3), PMePh2 (4), PEtPh2 (5); R'= Pr (6), Bu (7), PR3= PMe2Ph) are thermolyzed in solution by^-elimination processes liberating alkaneand alkene in a 1: 1 ratio. Kinetic studies on thermolysis of trans-[PdEt2 (PR3) 2] revealed that they decompose obeying the first-order rate law with respect to the concentration of the palladium complexes. Thermolysis predominantly proceeds from the four-coordinated complex without dissociation of the tertiary phosphine ligand. The minor parallel thermolysis pathway involving the dissociation of the phosphine is completely blocked by addition of the phosphine. Activation enthalpies for thermolysis of the ethylpalladium complexes having various steric bulkiness were