New octahedral RuCl2(CO)(L)[eta(2)-(P,O)-ketophosphane] complexes containing one hemilabile ketophosphane ligand

Authors
Citation
B. Demerseman, New octahedral RuCl2(CO)(L)[eta(2)-(P,O)-ketophosphane] complexes containing one hemilabile ketophosphane ligand, EUR J INORG, (9), 2001, pp. 2347-2359
Citations number
18
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
ISSN journal
1434-1948 → ACNP
Issue
9
Year of publication
2001
Pages
2347 - 2359
Database
ISI
SICI code
1434-1948(200109):9<2347:NORCC>2.0.ZU;2-0
Abstract
The reaction of the ketophosphanes Ph2PCH2C(=O)tBu (1), Ph2PCMe2C(=O)iPr (1 '), or Ph2PCMe2CH2C(=O)Me (1 ") with a precursor complex RuCl2(L)(eta (6)- p-cymene) [L = PMe3 (a), PMePh2 (b), PiPrPh(2) (c), PPh3 (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)-RuCl2(CO)(L)[eta (2)-(P,O)-ketophosph ane] (2a-e, 2 'a,e,f, and 2 "a) with traps-chlorine and traps-phosphorus at oms. Further reaction with carbon monoxide or acetonitrile under thermal ac tivation yields the cis,cis,trans derivatives (cct)RuCl2(CO)(2)(L)[eta (1)- (P)-ketophosphane] 4a,b and 4 'a, and (cct)-RuCl2(CO)(MeCN)(L)[eta (1)-(P)- ketophosphane] 5a,b,d. Complexes 2a,b and 2 'a rearrange under thermal acti vation, or after exposure to sunlight, into the (ctc and ccc)- RuCl2(CO)(L) [eta (2)-(P,O)-ketophosphane] isomers, with cis-chlorine and cis-phosphorus atoms, 6a,b and 8 'a, respectively. Complexes 6a,b reversibly add one mole cule of carbon monoxide when forming the all-cis derivatives (ccc)RuCl2(CO) (2)(L)[eta (1)-(P)-ketophosphane] 7a,b, respectively. The removal of one ch loride ligand in complexes 4a, 4 'a, or 5a with silver tetrafluoroborate af fords the stable cationic derivatives [RuCl(CO)(L ')(PMe3)[eta (2)-(PO)-ket ophosphane]][BF4], 8a and 8 'a (L ' = CO) and 9a (L ' = MeCN), respectively . Mild basic conditions are sufficient to allow the synthesis of the enolat ophosphane derivatives (ttt)-RuCl(CO)(2)(L)[eta (2)-(P,O)Ph2PCH=C(tBu)O], 1 0a,c,e, and of the analogous (ccc) and (cct) isomers, 11a,b and 12a, respec tively.