REACTIONS OF 2-COORDINATE PHOSPHINE PLATINUM(O) AND PALLADIUM(O) COMPOUNDS - LIGAND-EXCHANGE AND REACTIVITIES TOWARD SMALL MOLECULES
REACTIONS OF 2-COORDINATE PHOSPHINE PLATINUM(O) AND PALLADIUM(O) COMPOUNDS - LIGAND-EXCHANGE AND REACTIVITIES TOWARD SMALL MOLECULES
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DOI：
10.1021/ja00449a019
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
OTSUKA, S
中科院分区：
文献类型：
--
作者：
YOSHIDA, T;OTSUKA, S
Reactions of two-coordinate complexes PdL2 (1, L= P (z-Bu) 3; 2, L= PPh (z-Bu) 2; 3, L= Pfc-CeH) i) 3) and PtL2 (4, L= P (Z-Bu) 3; 5, L= PPh (Z-Bu) 2; 6, L= Pic-CeH 11) 3; 7, L= P (z-Pr) 3) were studied. The thermal reaction of 2 and 5 gives no evidence forortho C metalation. Ligand exchange of 2 and 5 with PPh (z-Bu) 2takes place through an associative mechanism at high temperature with activation energies of 7.8 and 12.1 kcal mol-1, respectively. These complexes, except 1 and 4, are sensitive to dioxygen and react even in the solid state to produce MO2L2. Dioxygen coordination in Pd02 [PPh (z-Bu) 2] 2 is reversible, while that in the corresponding Pt complex is irreversible. 1 reacts very slowly with dioxygen to give a red polynuclear oxygen-containing compound of formula [PdOP (Z-Bu) 3]„. The reaction of 1, 2, and 5 with CO gives M3 (CO) 3L3 (= Pd, L= P (z-Bu) 3, PPh (z-Bu) 2; M= Pt, L= PPh (Z-Bu) 2). Dimethyl fumarate (DF) with 2 or 5gives M (DF) 2PPh (z-Bu) 2 (M= Pd, Pt), while maleic anhydride (MA) affords M (MA)[PPh (Z-Bu) 2] 2. Oxidative addition of FIX (X= Cl, OCOCF3) to 1, 2, and 5 produces z/wzs-MH (X) L2 (M= Pd, L= P (z-Bu) 3, PPh (z-Bu) 2; M= Pt, L= PPh (z-Bu) 2). MeOFl reacts with PtL2 to give stable dihydride complexes tz-azz. i-PtH2L2 (L= PPh (Z-Bu) 2, Pfc-CiHi 1) 3, P (z-Pr) 3), which can be obtained also by mo-lecular hydrogen addition to the appropriate PtL2 at room temperature under normal pressure. 4 and 5 do not add FI2. All the
