Fundamentals of H2 Binding and Reactivity on Transition Metals Underlying Hydrogenase Function and H2 Production and Storage

Reactions of transition metal dihydrogen complexes

Publisher Summary The chemistry of metal–alkynyl compounds is developing at a rapid pace. The bonds of alkynyl ligands, like those of organic alkynes have been shown to participate in a rich set of chemical transformations. Electronic-absorption band maxima and extinction coefficients have been reported for a large number of metal–alkynyl complexes. Casual comparisons of electronic-absorption band energies or intensities among a series of compounds in the absence of such experiments are not without the risk of misinterpretation because a variety of important effects not associated with the presence or absence of M-CCR π-bonding may be operative such as mixings between electronic states of identical symmetry but different orbital character. The best and simplest means of placing the M–C bond distances of metal–alkyl complexes in a context that allows insight into whether or not they manifest M-CCR π-interactions is to compare them to M–C bond distances of complexes where such effects are expected to be insignificant, as for metal–alkynyl compounds.

The Bonding of Metal-Alkynyl Complexes

Synthesis and reactivity of Ru-, Os-, Rh-, and Ir-halide-sulfoxide complexes.

Structural diversity in coordination chemistry of tridentate and tetradentate polyphosphines of Group 6 to 10 transition metal complexes

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 2. X-ray structure determination of the novel compound Ru(CCPh)(.eta.3-PhC3CHPh)(Cyttp) (Cyttp = C6H5P(CH2CH2CH2P(c-C6H11)2)2)

A series of ruthenium(II) acetate complexes were synthesized and characterized by 31 P{ 1 H}, 1 H, and 13 C{ 1 H} NMR and IR spectroscopy. Treatment of RuCl 2 (Cyttp) (Cyttp=PhP(CH 2 CH 2 CH 2 P(c-C 6 H 11 ) 2 ) 2 ) with 1 equiv of AgO 2 CMe at room temperature gives mer-RuCl(O 2 CMe)(Cyttp) and with excess NaO 2 CMe in refluxing methanol produces fac-RuCl(O 2 CMe)(Cyttp)

Synthesis and characterization of ruthenium acetate complexes containing triphosphines

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 7. X-ray structures of syn-mer-RuCl(.eta.3-PhC3CHPh)(Cyttp).cntdot.1/2C6H6, anti-mer-RuCl(.eta.3-PhC3CHPh)(Cyttp), and mer-Ru(C.tplbond.CPh)(.eta.3-PhC3CHPh)(Cyttp)

The hydride complex RuH(BH{sub 4})(Cyttp) was produced from the reaction of RuCl{sub 2}(Cyttp) with excess NaBH{sub 4}. A series of six-coordinate RuHCl(L)(Cyttp) complexes (L = CO, P(OMe){sub 3}, CH{sub 3}CN) were synthesized from RuHCl(Cyttp), which was prepared from the reaction of RuCl{sub 2}(Cyttp) and excess lithium hydride in THF. Ruthenium dihydride complexes RuH{sub 2}(L)(Cyttp) (L = CO, N{sub 2}, CNCH{sub 2}C{sub 6}H{sub 5}, P(OMe){sub 3}, and P(OPh){sub 3}) were synthesized from RuH{sub 2}(H{sub 2})(Cyttp), which was prepared from the reaction of RuCl{sub 2}(Cyttp) with NaH in THF under a H{sub 2} atmosphere. The new compounds were characterized by microanalyses and infrared and {sup 1}H and {sup 31}P NMR spectroscopy. The crystal structure of RuII{sub 2} (N{sub 2})(Cyttp) was determined and is reported here.

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 3. Synthesis and characterization of new ruthenium hydride complexes containing C6H5P (CH2CH2CH2P (c-C6H11)2)2 (Cyttp)

Guochen Jia

Papers

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 2. X-ray structure determination of the novel compound Ru(CCPh)(.eta.3-PhC3CHPh)(Cyttp) (Cyttp = C6H5P(CH2CH2CH2P(c-C6H11)2)2)

Synthesis and characterization of ruthenium acetate complexes containing triphosphines

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 7. X-ray structures of syn-mer-RuCl(.eta.3-PhC3CHPh)(Cyttp).cntdot.1/2C6H6, anti-mer-RuCl(.eta.3-PhC3CHPh)(Cyttp), and mer-Ru(C.tplbond.CPh)(.eta.3-PhC3CHPh)(Cyttp)

Synthesis and reactivity of ruthenium hydride complexes of chelating triphosphines. 3. Synthesis and characterization of new ruthenium hydride complexes containing C6H5P (CH2CH2CH2P (c-C6H11)2)2 (Cyttp)

Isomerization of rucl2(cyttp)(cyttp=c6h5p(ch2ch2ch2p(c6h11)2)2) in solution