Formation of Osmium Alkylidene, Alkylidyne, and Dinitrogen Complexes from Reactions of OsCl2(PPh3)3 with Diazoalkanes

被引:1
作者
Cui, Mingxu [1 ]
Sung, Herman H. Y. [1 ]
Williams, Ian D. [1 ]
Jia, Guochen [1 ,2 ]
机构
[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong 0000, Peoples R China
[2] HKUST Shenzhen Res Inst, Shenzhen 518057, Peoples R China
基金
中国国家自然科学基金;
关键词
TRANSITION-METAL-COMPLEXES; RAY CRYSTAL-STRUCTURE; C-H ACTIVATION; MOLECULAR-STRUCTURE; CARBENE COMPLEXES; ARENEOSMIUM(II) COMPLEXES; RHODIUM(I) COMPLEXES; DIHYDROGEN COMPLEX; HYDROGEN MIGRATION; HYDRIDE-ALKYLIDYNE;
D O I
10.1021/acs.organomet.1c00536
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reactions of OsCl2(PPh3)(3) with a series of diazoalkanes were investigated. The reactions with monosubstituted diazoalkanes N2CHR gave the desired osmium alkylidene complexes OsCl2(= CHR)(PPh3)(2), the stability of which is dependent on the substituent on the alkylidene carbons. The five- coordinate osmium alkylidene complex OsCl2(= CHCOOMe)(PPh3)(2) is thermally stable, whereas the analogous complex OsCl2(=CH-p-tol)( PPh3)(2) readily rearranges to its hydrido-alkylidyne form OsHCl2( C-p-tol)(PPh3)(2). A substitution reaction of OsCl2(= CHCOOMe)(PPh3)(2) with PCy3 produced the hydrido-alkylidyne complex OsHCl2( CCOOMe)(PCy3)(2), revealing the effect of the phosphine on the relative stability of OsCl2(= CHCOOMe)(PR3)(2) and OsHCl2( CCOOMe)(PR3)(2). The reaction of OsCl2(PPh3)(3) with the acceptoracceptor disubstituted diazoalkane dibenzoyl diazomethane, bearing COPh substituents, led to the formation of the metallacyclic complex OsCl2{kappa(2)-N,O-[N2C(COPh)C(Ph)O]}(PPh3)(2) due to the chelating effect of dibenzoyl diazomethane. The complex OsCl2(PPh3)(3) catalyzed the homocoupling of the diazoalkane N2CPh2 to give the azine Ph2C = N-N = CPh2. The eta(1)-N-2 coordinated binuclear complex (Ph3P)(2)ClOs(mu-Cl)(3)Os(PPh3)(2)(N-2) was isolated as a minor product, which was considered to be an off-cycle product in the catalytic reaction.
引用
收藏
页码:3833 / 3842
页数:10
相关论文
共 104 条
  • [1] Addison A. W., SYNTHESIS STRUCTURE
  • [2] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE
    ADDISON, AW
    RAO, TN
    REEDIJK, J
    VANRIJN, J
    VERSCHOOR, GC
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07): : 1349 - 1356
  • [3] Preparation of diazoalkane complexes of osmium(II)
    Albertin, G
    Antoniutti, S
    Bordignon, E
    Carrera, B
    [J]. INORGANIC CHEMISTRY, 2000, 39 (20) : 4646 - 4650
  • [4] Pentamethylcyclopentadienyl osmium complexes that contain diazoalkane, dioxygen and allenylidene ligands: preparation and reactivity
    Albertin, Gabriele
    Antoniutti, Stefano
    Castro, Jesus
    Sibilla, Francesca
    [J]. DALTON TRANSACTIONS, 2019, 48 (09) : 3116 - 3131
  • [5] Preparation and reactivity of half-sandwich organic azide complexes of osmium
    Albertin, Gabriele
    Antoniutti, Stefano
    Castro, Jesus
    Ganz, Verena
    Sibilla, Francesca
    [J]. DALTON TRANSACTIONS, 2018, 47 (33) : 11658 - 11668
  • [6] Preparation of half-sandwich diazoalkane complexes of osmium
    Albertin, Gabriele
    Antoniutti, Stefano
    Forcolin, Matia
    Gasparato, Dario
    [J]. POLYHEDRON, 2016, 104 : 46 - 51
  • [7] Belkova NV, 2012, SPEC PER REP SPECTRO, V43, P1, DOI 10.1039/9781849734899-00001
  • [8] Group VIII Coordination Chemistry of a Pincer-Type Bis(8-quinolinyl)amido Ligand
    Betley, Theodore A.
    Qian, Baixin A.
    Peters, Jonas C.
    [J]. INORGANIC CHEMISTRY, 2008, 47 (24) : 11570 - 11582
  • [9] BOHLE DS, 1988, J ORGANOMET CHEM, V358, P411
  • [10] TERMINAL METHYLENE COMPLEXES OF RUTHENIUM(II) AND OSMIUM(II) AND INTRAMOLECULAR METHYLENE AND ACYL LIGAND COMBINATION TO FORM METALLAOXETENES - THE CRYSTAL-STRUCTURES OF [OSCL(ETA-2-C[O]-ORTHO-TOLYL)(=CH2)(PPH3)2] AND [RU(=C[PH]OCH2)(CN-PARA-TOLYL)2(PPH3)2]CIO4
    BOHLE, DS
    CLARK, GR
    RICKARD, CEF
    ROPER, WR
    SHEPARD, WEB
    WRIGHT, LJ
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (08) : 563 - 565