Further evidence supporting an inner sphere mechanism in the NO reduction of the copper(II) complex Cu(dmp)2(2+) (dmp=2,9-dimethyl-1,10-phenanthroline).

Described are further studies directed towards elucidating the mechanism of the nitric oxide reduction of the copper(II) model system, Cu(dmp)2(2+) (I, dmp=2,9-dimethyl-1,10-phenanthroline). The reaction of I with NO in methanol results in the formation of Cu(dmp)2+ (II) and methyl nitrite (CH3ONO), with a second order rate constant kNO=38.1 M-1 s-1 (298K).

Synthesis and crystal structures of (fulvalene)W(2)(SH)(2)(CO)(6), (fulvalene)W(2)(mu-S(2))(CO)(6), and (fulvalene)W(2)(mu-S)(CO)(6): low valent tungsten carbonyl sulfide and disulfide complexes stabilized by the bridging fulvalene ligand.

Reaction of FvW(2)(H)(2)(CO)(6) with 2/8S(8) in THF results in rapid and quantitative formation of FvW(2)(SH)(2)(CO)(6). The crystal structure of this complex is reported and shows that the two tungsten-hydrosulfide groups are on opposite faces of the fulvalene ligand in an anti configuration. Nevertheless, treatment of FvW(2)(SH)(2)(CO)(6) (1) with PhN[double bond]NPh produces FvW(2)(mu-S(2))(CO)(6) (2) and Ph(H)NN(H)Ph.

Reaction of *NO Thiolate and Thiol Complexes: Elimination of PhSNO from W(phen)(CO)(2)(SPh)(2), CO from W(phen)(CO)(2)((-S)(2)Arene), and HNO from W(phen)(CO)(3)(RSH).

Reaction of *NO with W(phen)(CO)(2)(SPh)(2) (phen = 1,10-phenanthroline) results in clean conversion to W(phen)(CO)(2)(NO)(SPh). Reduction of the W(II) bisthiolates to the W(0) nitrosyl thiolate occurs with simultaneous reductive elimination of PhS-NO, which is unstable but could be detected spectroscopically. Reaction of W(phen)(CO)(2)(1,2-S(2)-Arene), however, does not result in reductive elimination of either free or bound nitrosothiol.

Kinetic and Thermodynamic Studies of Reaction of *Cr(CO)(3)C(5)Me(5), HCr(CO)(3)C(5)Me(5), and PhSCr(CO)(3)C(5)Me(5) with *NO. Reductive Elimination of Thermodynamically Unstable Molecules HNO and RSNO Driven by Formation of the Strong Cr-NO Bond.

Reaction of H-Cr(CO)(3)C(5)Me(5) with *NO at 1-2 atm pressure in toluene solution yields Cr(NO)(CO)(2)C(5)Me(5) as the sole metal-containing product in addition to N(2)O and HNO(2) as the principle nitrogen-containing products. N(2)O and HNO(2) are attributed to decomposition of the initial product HNO. Kinetic studies yield the rate law d[P]/dt = -k(2nd)( )(order)[HCr(CO)(3)C(5)Me(5)][*NO]; k(2nd)( )(order) = 0.

Mechanistic Study of the Reaction of (*)Cr(CO)(3)C(5)Me(5) with H(2)S Yielding HCr(CO)(3)C(5)Me(5), HSCr(CO)(3)C(5)Me(5), and C(5)Me(5)(CO)(2)Cr=S=Cr(CO)(2)C(5)Me(5). Kinetic Evidence for Formation of the Substituted Radical Complex (*)Cr(CO)(2)(H(2)S)C(5)Me(5).

Reaction of a large excess of H(2)S with 2 mol of (*)Cr(CO)(3)C(5)Me(5) yields HCr(CO)(3)C(5)Me(5) and HSCr(CO)(3)C(5)Me(5). Kinetic studies of this reaction show two reaction pathways are followed. At pressures of CO above 10-15 atm and temperatures View Article and Find Full Text PDF

The Enthalpy of Insertion of Sulfur into the Metal-Hydrogen Bond. Synthetic, Structural, and Calorimetric Study of the Complexes HS-M(CO)(3)C(5)R(5) [M = Cr, Mo, W; R = H, Me].

Synthetic and calorimetric studies of the sulfhydryl complexes HS-M(CO)(3)C(5)R(5) (M = Cr, R = Me; M = Mo, W, R = H, Me) are reported. The Mo and W complexes can be obtained in high yield by reaction of the hydrido complexes H-M(CO)(3)C(5)R(5) with Ph(3)Sb=S, which readily undergoes single S atom transfer to the metal-hydrogen bond yielding the metal-sulfhydryl complex. Direct reaction between the metal hydrides and a limited amount of sulfur also yields the sulfhydryl complexes as the dominant organometallic product.