Stolzenberg Alan M, Workman Sarah R, Gutshall Jessica E, Petersen Jeffrey L, Akhmedov Novruz
Department of Chemistry, West Virginia University, Morgantown, WV 26506, USA.
Inorg Chem. 2007 Aug 6;46(16):6744-54. doi: 10.1021/ic070251+. Epub 2007 Jul 7.
Reactions of cobaloxime Na[(t-BuPy)Co(DH)2] with Ph3ECl (E = Si, Ge, Sn, and Pb) were investigated. Metal-metal bonded complexes (t-BuPy)Co(DH)2EPh3 were isolated for E = Sn and Pb. (t-BuPy)Co(DH)2SnPh3.(C2H5)2O, C39H52CoN5O5Sn, crystallized in the monoclinic space group P21/c (Z = 4) with unit cell dimensions a = 11.6443(6) A, b = 15.6085(8) A, c = 22.6354(12) A, beta = 96.634(1) degrees , and V = 4086.4(4) A3 at 295(2) K. The structure resembled those of six-coordinate alkyl cobaloxime complexes and had Co-NPy and Co-Sn distances of 2.056(2) and 2.5568(3) A, respectively. (t-BuPy)Co(DH)2PbPh3, C35H42CoN5O4Pb, crystallized in the monoclinic space group P21/n (Z = 4) with unit cell dimensions a = 15.0104(7) A, b = 15.7693(8) A, c = 16.6230(8) A, beta = 114.348(1) degrees , and V = 3584.8(3) A3 at 295(2) K. The complex was nearly isostructural with the Sn analogue and had Co-NPy and Co-Pb distances of 2.049(2) and 2.6191(4) A, respectively. Coupling of the ortho phenyl protons to the spin 1/2 isotopes of Sn and of Pb was a characteristic feature of the 1H NMR spectrum. Additional, longer range couplings were observed for the Pb complex and for both complexes in the 13C NMR. Metal-metal bonded complexes were not obtained for E = Si or Ge. The products isolated in the latter case were the hydride Ph3GeH and the cobalt(II) complex (t-BuPy)Co(DH)2,C17H27CoN5O4, which crystallized in the orthorhombic space group Pbcn (Z = 8). Unit cell dimensions were a = 17.9821(11) A, b = 9.7449(6) A, c = 22.7374(15) A, and V = 3984.4(4) A3 at 295(2) K. The five-coordinate complex had Co-NPy = 2.096(2) A and was dimeric in the lattice.
研究了钴肟钠[（叔丁基吡啶）钴（DH）₂]与Ph₃ECl（E = Si、Ge、Sn和Pb）的反应。对于E = Sn和Pb，分离得到了金属-金属键合配合物（叔丁基吡啶）钴（DH）₂EPh₃。（叔丁基吡啶）钴（DH）₂SnPh₃·（C₂H₅）₂O，C₃₉H₅₂CoN₅O₅Sn，在单斜空间群P2₁/c（Z = 4）中结晶，在295（2）K时，晶胞参数a = 11.6443（6）Å，b = 15.6085（8）Å，c = 22.6354（12）Å，β = 96.634（1）°，V = 4086.4（4）ų。其结构类似于六配位烷基钴肟配合物，Co-NPy和Co-Sn距离分别为2.056（2）和2.5568（3）Å。（叔丁基吡啶）钴（DH）₂PbPh₃，C₃₅H₄₂CoN₅O₄Pb，在单斜空间群P2₁/n（Z = 4）中结晶，在295（2）K时，晶胞参数a = 15.0104（7）Å，b = 15.7693（8）Å，c = 16.6230（8）Å，β = 114.348（1）°，V = 3584.8（3）ų。该配合物与Sn类似物几乎同构，Co-NPy和Co-Pb距离分别为2.049（2）和2.6191（4）Å。邻位苯基质子与Sn和Pb的自旋1/2同位素的耦合是¹H NMR谱的一个特征。此外，在¹³C NMR中观察到了Pb配合物以及两种配合物的额外的长程耦合。对于E = Si或Ge，未得到金属-金属键合配合物。在后一种情况下分离得到的产物是氢化物Ph₃GeH和钴（II）配合物（叔丁基吡啶）钴（DH）₂，C₁₇H₂₇CoN₅O₄，它在正交空间群Pbcn（Z = 8）中结晶。在295（2）K时，晶胞参数a = 17.9821（11）Å，b = 9.7449（6）Å，c = 22.7374（15）Å，V = 3984.4（4）ų。该五配位配合物的Co-NPy = 2.096（2）Å，在晶格中为二聚体。
