摘要 : A slow reaction consisting of a cleavage of one Ru-Cl bond occurred when a mixture of RuCl_2[Ph_2PCH_2C(tBu)=O]_2 (1) and [NH_4][PF_6] was dissolved in methanol as shown by a subsequent reaction with carbon monoxide affording the ... 展开 A slow reaction consisting of a cleavage of one Ru-Cl bond occurred when a mixture of RuCl_2[Ph_2PCH_2C(tBu)=O]_2 (1) and [NH_4][PF_6] was dissolved in methanol as shown by a subsequent reaction with carbon monoxide affording the stable cationic derivative {RuCl(CO)[Ph_2PCH_2C(tBu)=O]_2}[PF_6] (2). By contrast, the straightforward reaction of 1 with carbon monoxide yielded RuCl_2(CO)[Ph_2PCH_2C(tBu)=O][Ph_2PCH_2C(=O)tBu] (3) which contains unreactive Ru-Cl bonds. The isomerization of 2, which is induced under sun light exposure, is the preliminary step to the selective formation of the all-cis bis(enolato-phosphane) derivative (ccc)-Ru(CO)_2[#eta#~2-(P,O)-Ph_2PCH=C(tBu)O]_2 (9). The isomeric bis(enolato-phosphane) derivative (cct)-Ru(CO)_2[#eta#~2-(P,O)Ph_2PCH=C(tBu)O]_2 (10), with trans phosphorus and cis carbonyl ligands, respectively, was selectively obtained under mild basic conditions, starting from (cct)-RuCl_2(CO)_2[Ph_2PCH_2C(=O)tBu]_2 (4), which results from the reaction of 3 with carbon monoxide under thermal activation. Through an oxidative addition process, the reaction of 1 with [NO][BF_4] yielded {Rucl_2(NO)[Ph_2PCH_2C(tBu)=O][Ph_2PCH_2C(=O)tBu]}[BF_4] (13) with trans phosphorus and trans chloride ligands, respectively. Simple deprotonation of 13 generated the enolato-phosphane Ru~(IV) complex RuCl_2(NO)[Ph_2PCH=C(tBu)O][Ph_2PCH_2C(=O)tBu] (14) which retains the same geometry. Under basic conditions, the bis(enolato-phosphane) derivative RuCl(NO)[#eta#~2-P,O)-Ph_2PCH=C(tBu)O]_2 (15) was obtaned. The formation of 15 surprisingly showed a trans to cis rearrangement of the two phosphorus coordinating atoms, as further confirmed by an X-ray structure determination. 收起