八面体钌（II）酰胺配合物TpRu（L）（L'）（NHR）（Tp = 氢三（吡唑基）硼酸酯；L = L' = 三甲基磷酸酯或三甲基膦或L = CO且L' = 三苯基膦；R = H、苯基或叔丁基）：合成、表征以及与弱酸性C-H键的反应

Octahedral Ru(II) amido complexes TpRu(L)(L')(NHR) (Tp = hydridotris(pyrazolyl)borate; L = L' = P(OMe)3 or PMe3 or L = CO and L' = PPh3; R = H, Ph, or tBu): synthesis, characterization, and reactions with weakly acidic C-H bonds.

作者信息

Conner David, Jayaprakash K N, Wells Michael B, Manzer Selena, Gunnoe T Brent, Boyle Paul D

机构信息

Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.

出版信息

Inorg Chem. 2003 Jul 28;42(15):4759-72. doi: 10.1021/ic034410a.

DOI:10.1021/ic034410a

PMID:12870969

Abstract

The octahedral Ru(II) amine complexes [TpRu(L)(L')(NH(2)R)][OTf] (L = L' = PMe(3), P(OMe)(3) or L = CO and L' = PPh(3); R = H or (t)Bu) have been synthesized and characterized. Deprotonation of the amine complexes [TpRu(L)(L')(NH(3))][OTf] or [TpRu(PMe(3))(2)(NH(2)(t)Bu)][OTf] yields the Ru(II) amido complexes TpRu(L)(L')(NH(2)) and TpRu(PMe(3))(2)(NH(t)Bu). Reactions of the parent amido complexes or TpRu(PMe(3))(2)(NH(t)Bu) with phenylacetylene at room temperature result in immediate deprotonation to form ruthenium-amine/phenylacetylide ion pairs, and heating a benzene solution of the [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] ion pair results in the formation of the Ru(II) phenylacetylide complex TpRu(PMe(3))(2)(C[triple bond]CPh) in >90% yield. The observation that [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] converts to the Ru(II) acetylide with good yield while heating the ion pairs [TpRu(L)(L')(NH(3))][PhC(2)] yields multiple products is attributed to reluctant dissociation of ammonia compared with the (t)butylamine ligand (i.e., different rates for acetylide/amine exchange). These results are consistent with ligand exchange reactions of Ru(II) amine complexes [TpRu(PMe(3))(2)(NH(2)R)][OTf] (R = H or (t)Bu) with acetonitrile. The previously reported phenyl amido complexes TpRuL(2)(NHPh) [L = PMe(3) or P(OMe)(3)] react with 10 equiv of phenylacetylene at elevated temperature to produce Ru(II) acetylide complexes TpRuL(2)(C[triple bond]CPh) in quantitative yields. Kinetic studies indicate that the reaction of TpRu(PMe(3))(2)(NHPh) with phenylacetylene occurs via a pathway that involves TpRu(PMe(3))(2)(OTf) or [TpRu(PMe(3))(2)(NH(2)Ph)][OTf] as catalyst. Reactions of 1,4-cyclohexadiene with the Ru(II) amido complexes TpRu(L)(L')(NH(2)) (L = L' = PMe(3) or L = CO and L' = PPh(3)) or TpRu(PMe(3))(2)(NH(t)Bu) at elevated temperatures result in the formation of benzene and Ru hydride complexes. TpRu(PMe(3))(2)(H), [Tp(PMe(3))(2)Ru[double bond]C[double bond]C(H)Ph][OTf], [Tp(PMe(3))(2)Ru=C(CH(2)Ph)[N(H)Ph]][OTf], and [TpRu(PMe(3))(3)][OTf] have been independently prepared and characterized. Results from solid-state X-ray diffraction studies of the complexes [TpRu(CO)(PPh(3))(NH(3))][OTf], [TpRu(PMe(3))(2)(NH(3))][OTf], and TpRu(CO)(PPh(3))(C[triple bond]CPh) are reported.

摘要

已合成并表征了八面体Ru(II)胺配合物[TpRu(L)(L')(NH₂R)][OTf]（L = L' = PMe₃、P(OMe)₃ 或 L = CO且L' = PPh₃；R = H或(t)Bu）。胺配合物[TpRu(L)(L')(NH₃)][OTf]或[TpRu(PMe₃)₂(NH₂(t)Bu)][OTf]的去质子化反应生成Ru(II)酰胺配合物TpRu(L)(L')(NH₂)和TpRu(PMe₃)₂(NH(t)Bu)。母体酰胺配合物或TpRu(PMe₃)₂(NH(t)Bu)与苯乙炔在室温下反应会立即发生去质子化反应，形成钌-胺/苯乙炔离子对，并且加热[TpRu(PMe₃)₂(NH₂(t)Bu)][PhC₂]的苯溶液会生成产率大于90%的Ru(II)苯乙炔配合物TpRu(PMe₃)₂(C≡CPh)。观察到[TpRu(PMe₃)₂(NH₂(t)Bu)][PhC₂]在加热时能以良好的产率转化为Ru(II)乙炔化物，而加热离子对[TpRu(L)(L')(NH₃)][PhC₂]会生成多种产物，这归因于与叔丁胺配体相比氨的解离较慢（即乙炔化物/胺交换速率不同）。这些结果与Ru(II)胺配合物[TpRu(PMe₃)₂(NH₂R)][OTf]（R = H或(t)Bu）与乙腈的配体交换反应一致。先前报道的苯基酰胺配合物TpRuL₂(NHPh) [L = PMe₃ 或 P(OMe)₃]在高温下与10当量的苯乙炔反应，能定量生成Ru(II)乙炔化物配合物TpRuL₂(C≡CPh)。动力学研究表明，TpRu(PMe₃)₂(NHPh)与苯乙炔的反应通过一条涉及TpRu(PMe₃)₂(OTf)或[TpRu(PMe₃)₂(NH₂Ph)][OTf]作为催化剂的途径进行。1,4 - 环己二烯与Ru(II)酰胺配合物TpRu(L)(L')(NH₂)（L = L' = PMe₃ 或 L = CO且L' = PPh₃）或TpRu(PMe₃)₂(NH(t)Bu)在高温下反应会生成苯和Ru氢化物配合物。已独立制备并表征了TpRu(PMe₃)₂(H)、[Tp(PMe₃)₂Ru≡C≡C(H)Ph][OTf]、[Tp(PMe₃)₂Ru = C(CH₂Ph)[N(H)Ph]][OTf]和[TpRu(PMe₃)₃][OTf]。报道了配合物[TpRu(CO)(PPh₃)(NH₃)][OTf]、[TpRu(PMe₃)₂(NH₃)][OTf]和TpRu(CO)(PPh₃)(C≡CPh)的固态X射线衍射研究结果。