ISSN:
1434-1948
Keywords:
Ruthenium
;
Phosphorus
;
Triphos complexes
;
Fluxionality
;
Arm-off dissociation
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Structural fluxionality is apparent in the 1H- and 31P-NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF3SO3), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ2N,S coordinating thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CN-; 8, n = 0, Y = H-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2 molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9, which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)], 10, on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. A similar κ3P→κ2P arm-off dissociation leads to the formation of [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) and [Ru(mmim-κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ2N,S)(MeCN)(triphos-κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.
Type of Medium:
Electronic Resource
