摘要 : The reaction of the ketophosphanes Ph_2PCH_2C(=O)tBu (1), Ph_2PCMe_2C(=O)iPr (1'), or Ph_2PCMe_2CH_2C(=O)Me (1") with a precursor complex RuCl_2(L)(#eta#~6-p-cymene) [L = PMe_3 (a), PMePh_2 (b), PiPrPh_2 (c), PPh_3 (d), P(OMe)Ph_2... 展开 The reaction of the ketophosphanes Ph_2PCH_2C(=O)tBu (1), Ph_2PCMe_2C(=O)iPr (1'), or Ph_2PCMe_2CH_2C(=O)Me (1") with a precursor complex RuCl_2(L)(#eta#~6-p-cymene) [L = PMe_3 (a), PMePh_2 (b), PiPrPh_2 (c), PPh_3 (d), P(OMe)Ph_2 (e), P(OMe)_3 (f)] in methanol and under carbon monoxide, provides an access to a novel family of complexes (ttt)-RuCl_2(CO)(L)[#eta#~2-(P,O)-ketophosphane] (2a-e, 2'a,e,l, and 2"a) with trans-chlorine and trans-phosphorus atoms. Further reaction with carbon monoxide or acetonitrile under thermal activation yields the cis,cis,trans derivatives (cct)-RuCl_2(CO)_2(L)[#eta#~1-(P)-ketophosphane] 4a,b and 4'a, and (cct)-RuCl_2(CO)(MeCN)(L)[#eta#~1-(P)-ketophosphane] Sa,b,d. Complexes 2a,b and 2'a rearrange under thermal activation, or after exposure to sunlight, into the (ctc and ccc)-RuCl_2(CO)(L)[#eta#~2-(P,O)-ketophosphane] isomers, with cis-chlorine and cis-phosphorus atoms, 6a,b and 6'a, respectively. Complexes 6a,b reversibly add one molecule of carbon monoxide when forming the all-cis derivatives (ccc)- RuCl_2(CO)_2(L)[#eta#~1-(P)-ketophosphane] 7a,b, respectively. The removal of one chloride ligand in complexes 4a, 4'a, or 5a with silver tetrafluoroborate affords the stable cationic derivatives {RuCl(CO)(L')(PMe_3)[#eta#~2-(P'O)-ketophosphane]}[BF_4], 8a and 8'a (L' = CO) and 9a (L' = MeCN), respectively. Mild basic conditions are sufficient to allow the synthesis of the enolatophosphane derivatives (ttt)-RuCl(CO)_2(L)[#eta#~2-(P,O)-Ph2_PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respectively. 收起