377775-65-0Relevant academic research and scientific papers
New octahedral RuCl2(CO)(L)[η2-(P,O)-ketophosphane] complexes containing one hemilabile ketophosphane ligand
Demerseman, Bernard
, p. 2347 - 2359 (2007/10/03)
The reaction of the ketophosphanes Ph2PCH2C(=O)tBu (1), Ph2PCMe2C(=O)iPr (1′), or Ph2PCMe2CH2C(=O)Me (1″) with a precursor complex RuCl2(L)(η6-p-cymene) [L = PMe3 (a), PMePh2 (b), PiPrPh2 (c), PPh3 (d), P(OMe)Ph2 (e), P(OMe)3 (f)] in methanol and under carbon monoxide, provides an access to a novel family of complexes (ttt)-RuCl2(CO)(L)[η2-(P,O)-ketophosphane] (2a-e, 2′a,e,f, 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)-RuCl2(CO)2(L)[η1-(P)- ketophosphane] 4a,b and 4′a, and (cct)-RuCl2(CO)(MeCN)(L)[η1-(P)-ketophosphane] 5a,b,d. Complexes 2a,b and 2′a rearrange under thermal activation, or after exposure to sunlight, into the (ctc and ccc)-RuCl2(CO)(L)[η2-(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)-RuCl2(CO)2(L)[η1-(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′)(PMe3)[η2-(P,O)- ketophosphane]}[BF4], 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)[η2-(P,O)-Ph2 PCH=C(tBu)O], 10a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respectively.
