Coordination behaviour of (diaryl disulfide)-bridged dinuclear thiairidaindan cores: ligand substitution by isocyanides, CO, hydrazines and hydroxylamine, and related reactions

Transition Metal Coordination Chemistry ofN,N-Bis(2-{pyrid-2-ylethyl})hydroxylamine

“…Of the previously elucidated complexes, only three compounds from the CCDC show N-bound hydroxylamine, as seen in [ trans -Ru(CO) (NH 2 OH)(PPh 3 ) 2 (S 2 CNEt 2 )][SO 3 CF 3 ], [ mer,trans -Re(CO) 3 (NH 2 OH)(PPh 3 ) 2 ][SO 3 CF 3 ], and [Ir(μ-SC 6 H 3 MeCH 2 )Cl(PPh 3 )(NH 2 OH)] 2. In these three structures, the N−O bond length measures 1.422(5), 1.45(1), and 1.432(5) Å, respectively. In gas phase hydroxylamine, the bond length is 1.453 Å, while in the inorganic salt [Ni(NH 2 OH) 6 ][SO 4 ] the average distance is 1.44 Å …”

“…Several fundamental questions remain concerning the nature of hydroxylamine as a ligand, including the site of metal binding (N or O) and the protonation state of the OH group upon coordination. Unsubstituted hydroxylamine, however, often does not form stable metal complexes; while there are many examples of transition metal catalyzed hydroxylamine reactions, there are only 22 structures of unmodified hydroxylamine bound to a metal ion in the Cambridge Crystallographic Data Centre (CCDC) database, incorporating the elements V, Co, Mo, , Ru, W, Re, Ir, and U . One methodology to get around this problem is to functionalize either the oxygen or the nitrogen with R groups, which can result in the formation of more stable complexes with metal ions.…”

Novel Sterically Hindered Substituted Ferrocenes and Their Transition Metal Complexes

“…Such examples are not just confined to copper complexes however, as the first example of this phenomenon occurred with a rhodium complex, [{Rh(η 5 -C 5 Me 5 )} 2 (PF 2 O 2 ) 3 ]PF 6 . There are also occurrences with iridium, [{Ir(μ-SC 6 H 2 Me 2 CH 2 )(PPh 3 )(XyNC)} 2 (μ-PF 2 O 2 )][PF 6 ]; ruthenium, [{Ru(IV)(POF 3 )[P(OMe) 3 ] 2 (μ-S)(μ-PF 2 O 2 ) 2 ]; and palladium, [Pd(μ-PF 2 O 2 )(dppomf + )] 2 . Although PF 6 - is usually stable, it is known to undergo hydrolysis to PF 2 O 2 - and PFO 3 2- in the presence of various acids, aquametal complexes, and transition metals. ,, The oxygen source in these reactions seems to be adventitious water rather than dioxygen .…”

“…There are also occurrences with iridium, [{Ir(μ-SC 6 H 2 Me 2 CH 2 )(PPh 3 )(XyNC)} 2 (μ-PF 2 O 2 )][PF 6 ]; ruthenium, [{Ru(IV)(POF 3 )[P(OMe) 3 ] 2 (μ-S)(μ-PF 2 O 2 ) 2 ]; and palladium, [Pd(μ-PF 2 O 2 )(dppomf + )] 2 . Although PF 6 - is usually stable, it is known to undergo hydrolysis to PF 2 O 2 - and PFO 3 2- in the presence of various acids, aquametal complexes, and transition metals. ,, The oxygen source in these reactions seems to be adventitious water rather than dioxygen . Matsumoto et al, on the basis of a mass spectrometry experiment using 18 O 2 , concluded that the oxygen atoms in the difluorophosphato ligand [{Ru(IV)(POF 3 )[P(OMe) 3 ] 2 (μ-S)(μ-PF 2 O 2 ) 2 ] are derived from a trace amount of water in the solvent .…”