Dickinson Paul W, Girolami Gregory S
School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, Illinois 61801, USA.
Inorg Chem. 2006 Jun 26;45(13):5215-24. doi: 10.1021/ic0602291.
Treatment of H2OsBr6 with excess 1,5-cyclooctadiene (cod) in boiling tert-butyl alcohol affords the polymer [OsBr2(cod)]x (1), which reacts with acetonitrile to form the mononuclear adduct OsBr2(cod)(CH3CN)2 (2). Polymer 1 reacts with potassium trispyrazolylborate (KTp) in ethanol to afford the hydride TpOs(cod)H (3) and the bromide complex TpOs(cod)Br (4). Bromide complex 4 reacts with sodium methoxide in methanol to afford TpOs(cod)OMe (5), which has been structurally characterized. Treatment of hydride 3 with methyl trifluoromethanesulfonate (MeOTf) in diethyl ether results in loss of methane and formation of the triflate complex TpOs(cod)OTf (6), which reacts with MgMe2 to give the methyl complex TpOs(cod)Me (7). The addition of bis(dimethylphosphino)methane (dmpm) to the known compound TpOs(PPh3)2Cl yields a mixture of the substitution products TpOs(eta1-dmpm)(PPh3)Cl (8) and TpOs(eta2-dmpm)Cl (9); the latter reacts with methyllithium to generate the methyl compound TpOs(dmpm)Me (10). NMR and IR data for these new compounds are reported. Crystal data for 5.MeOH at -80 degrees C are as follows: monoclinic, P2(1)/n, a = 10.728(1) A, b = 14.004(2) A, c = 13.906(2) A, beta = 102.42(6) degrees , V = 2040.3(5) A3, Z = 4, R(F) = 0.0247 for I > or = 2sigma(I), and R(wF2) = 0.0539 for all data.
在沸腾的叔丁醇中，用过量的1,5 - 环辛二烯（cod）处理H2OsBr6，得到聚合物[OsBr2(cod)]x（1），它与乙腈反应形成单核加合物OsBr2(cod)(CH3CN)2（2）。聚合物1在乙醇中与三（吡唑基）硼酸钾（KTp）反应，得到氢化物TpOs(cod)H（3）和溴化物配合物TpOs(cod)Br（4）。溴化物配合物4在甲醇中与甲醇钠反应，得到已进行结构表征的TpOs(cod)OMe（5）。在乙醚中用甲基三氟甲磺酸酯（MeOTf）处理氢化物3，导致甲烷损失并形成三氟甲磺酸酯配合物TpOs(cod)OTf（6），它与MgMe2反应生成甲基配合物TpOs(cod)Me（7）。向已知化合物TpOs(PPh3)2Cl中加入双（二甲基膦基）甲烷（dmpm），得到取代产物TpOs(η1 - dmpm)(PPh3)Cl（8）和TpOs(η2 - dmpm)Cl（9）的混合物；后者与甲基锂反应生成甲基化合物TpOs(dmpm)Me（10）。报道了这些新化合物的NMR和IR数据。5·MeOH在 - 80℃时的晶体数据如下：单斜晶系，P2(1)/n，a = 10.728(1) Å，b = 14.004(2) Å，c = 13.906(2) Å，β = 102.42(6)°，V = 2040.3(5) Å3，Z = 4，对于I≥2σ(I)，R(F) = 0.0247，对于所有数据，R(wF2) = 0.0539。
