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Fluxionality and Phosphane Arm‐off Reactions of Octahedral Ruthenium(II) Complexes with the Tripodal Polyphosphane MeC(CH 2 PPh 2 ) 3
Author(s) -
Landgrafe Claudia,
Sheldrick William S.,
Südfeld Marc
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199803)1998:3<407::aid-ejic407>3.0.co;2-p
Subject(s) - triphos , chemistry , ruthenium , octahedron , medicinal chemistry , dissociation (chemistry) , crystal structure , stereochemistry , acetone , crystallography , nuclear magnetic resonance spectroscopy , nmr spectra database , molecule , catalysis , spectral line , organic chemistry , physics , astronomy
Structural fluxionality is apparent in the 1 H‐ and 31 P‐NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF 3 SO 3 ), 2 − 5 , at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ 2 N , S coordinating thioamide. In contrast, complexes [Ru(Et 2 NCS 2 )(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)](CF 3 SO 3 ) 2 , 1 , with Na(Et 2 NCS 2 ) at a 1:2 molar ratio yields [Ru(Et 2 NCS 2 ‐κ 2 S )(Et 2 NCS 2 ‐κ S )(triphos)], 9 , which slowly converts to [Ru(Et 2 NCS 2 ‐κ 2 S ) 2 (triphosO‐κ 2 P )], 10 , on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph) 2 CH 2 C(CH 3 )(CH 2 PPh 2 ) 2 ]. A similar κ 3 P →κ 2 P arm‐off dissociation leads to the formation of [Ru(mpy‐κ 2 N , S ) 2 (triphosO‐κ 2 P )] ( 13 ) and [Ru(mmim‐κ 2 N , S ) 2 (triphosO‐κ 2 P )] ( 14 ) (Hmpy = 2‐mercaptopyridine, Hmmim = 2‐mercapto‐1‐methylimidazole). Crystal structures are reported for [Ru(mbt‐κ 2 N , S )(MeCN)(triphos‐κ 3 P )](CF 3 SO 3 ) ( 4 ) (Hmbt = 2‐mercaptobenzothiazole), [Ru(mpym‐κ 2 N , S )(mpym‐κ S )(triphos‐κ 3 P )] ( 11 ) (Hmpym = 2‐mercaptopyrimidine) and 14 , the latter of which is present as the OC‐6‐13 isomer.