Assignment of MC Stretching and MCN Bending Frequencies in Metal Cyanide Complexes

Abstract

Inorganic Chemistry written, so that each forward process is favored by an increase of entropy but resisted by an increase of enthalpy. Every K value represents an average of at least two experiments. The datum for 42.23°in Table XI represents an average of log K and 1/7' at 38.8 and 46.7°.

Responses of the Fe(CN)2(CO) Unit to Electronic Changes as Related to Its Role in [NiFe]Hydrogenase

“…This is evidence of very weak vibrational coupling between the ν(CO) and ν(CN) modes. On the other hand, there is a small difference in the interaction force constant for the two CN moieties in the two environments, with the enzyme unit displaying a slightly larger interaction force constant ( k i ) of 0.079 vs 0.048 dyn/cm in the model complex. − …”

Synthesis of gold-(I) and -(III) complexes with carbonyl-stabilized phosphorus ylides. Crystal structure of [{Au(PPh3)}2{µ-C(PPh3)CO2Et}]ClO4

“…carbonyl-stabilized) ylides. Nevertheless the reaction of [AuCl(CH(PPh,)CO,R)] with the corresponding ylide in the presence of NaClO, leads to complexes [Au(CH(PPh,)CO,R),]ClO, [R = Me (11) or Et (12)]. In the absence of NaClO, this substitution does not occur.…”

“…and N.M.R. Spectra-The substitution of a hydrogen atom in the phosphonium cations by the groups AuL' (1)-(3), AuCl -(7), (8), or AuL (1 l), (12) promotes a decrease in the v(C0) stretching frequencies from 1 715 (R = Me), 1 720 (R = Et) to 168(r-1 690 cm-' (see Table 2). The replacement of both hydrogen atoms by two AuL' groups leads, as expected, to even lower v(C0) frequencies for the dinuclear complexes (1 630-1640 cm-I).…”

“…[Au{ CH(PPh3)C0,R},]C10, [R = Me(l1)or Et (12)]. -To solutions of complex (7) (200 mg, 0.35 mmol) or (8) (100 mg, 0.17 mmol) in acetone (10 cm3) were added successively equimolar amounts of solid Ph,PCHCO,Me or Ph,PCHCO,Et and NaClO,.…”

Dimethylgold(III) pseudohalides and their reactions with triphenylphosphine and triphenylarsine

“…The bands in 385-394-cm-1 region undoubtedly arise from Au-CN stretching and bending modes, and these frequencies are somewhat lower than in the inorganic gold(III) complexes, e.g., AuC12-(CN)2. 24,26 With this work, five compounds of the type (CH3)2-AuXP(CeH6)3 have been synthesized with X = Cl~, NCO-, NCS-, CN-, and P(C6Hb)3. These illustrate an interesting intensity effect observed with dimethylgold (III) compounds.…”