Syntheses and X-ray Diffraction Studies of Half-Sandwich Hydridosilyl Complexes of Ruthenium

The reactions of a series of half-sandwich trihydrides of ruthenium, Cp*(R3P)Ru(H)3 (R3P
= Pri3P, Pri2MeP, PriMe2P, PhMe2P), with a family of chlorosilanes (ClSiHMe2, Cl2SiHMe,
Cl3SiH) have been studed with the aim of preparing the dihydridesilyl derivatives Cp*(R3P)Ru(H)2(SiR3). The reaction of Cp*(R3P)Ru(H)3 with ClSiHMe2 occurs at 90 °C and gives
two types of products, Cp*(R3P)Ru(H)2(SiClMe2) (1) and Cp*(R3P)Ru(H)2(SiCl2Me) (2). The
yield of complexes 2 increases with the decrease of the size of the phosphine ligand. X-ray
structures of Cp*(Pri3P)Ru(H)2(SiClMe2) (1a) and Cp*(Pri2MeP)Ru(H)2(SiClMe2) (1b) are
consistent with the presence of interligand hypervalent interactions Ru−H···Si−Cl. The
compounds Cp*(R3P)Ru(H)(Cl)(SiCl2Me) (3) were prepared by the reaction of Cp*(R3P)Ru(H)3 with Cl2SiHMe at 60 °C and characterized by NMR and IR spectroscopy. Complex Cp*(Pri3P)Ru(Cl)(SiCl2Me)(H) (3a) reacts with excess PMe3 to give the H−Si elimination product
Cp*(PMe3)2RuCl. The reactions of Cp*(R3P)Ru(H)3 (R3P = Pri3P, Pri2MeP) with Cl2SiHMe
in the presence of NEt3 at 90 °C give the dihydridesilyls Cp*(R3P)Ru(H)2(SiCl2Me) (R3P =
Pri3P (2a), R3P = Pri2MeP (2b)). X-ray structures of these products may be rationalized as
containing a double interligand hypervalent interaction Ru−H2···Si−Cl2. NMR reaction
between Cp*(MePri2P)Ru(H)3 and excess Cl3SiMe at 100 °C resulted in a clean formation of
Cp*(MePri2P)Ru(H)(Cl)(SiCl2Me). Complexes Cp*(R3P)Ru(Cl)(SiCl3)(H) (5) were prepared by
the reaction of Cp*(R3P)Ru(H)3 with Cl3SiH at room temperature and characterized by NMR
and IR spectroscopy. The reactions of Cp*(R3P)Ru(H)3 (R3P = Pri3P, Pri2MeP) with Cl3SiH
in the presence of NEt3 at 60 °C give the dihydridesilyls Cp*(R3P)Ru(H)2(SiCl2H) (R3P =
Pri3P (6a), R3P = Pri2MeP (6b)) along with a mixture of some other compounds, whereas
the analogous reactions in the presence of NPri2Et afford the dihydridesilyls Cp*(R3P)Ru(H)2(SiClH2) (R3P = Pri3P (7a), R3P = Pri2MeP (7b)). Complex Cp*(Pri3P)RuH2(SiH3) (8a),
prepared by the reduction of Cp*(Pri3P)Ru(Cl)(SiCl3)(H) (5a) by LiAlH4, reacts with [NHMe2Ph]Cl to give a mixture of Cp*(Pri3P)Ru(H)3 and Cp*(Pri3P)Ru(H)2(SiClH2) (7a). The crystal
structures of 1a,1b, 2a, 2c, 5b, 5c, 5d, and 8a have been determined by X-ray structure
analysis.

本研究以制备二氢硅基衍生物Cp*(R3P)Ru(H)2(SiR3)为目标，对一系列钌半夹心三氢化物Cp*(R3P)Ru(H)3（其中R3P分别为三异丙基膦（Pri3P）、异丙基二甲基膦（Pri2MeP）、二异丙基甲基膦（PriMe2P）、苯基二甲基膦（PhMe2P））与一族氯硅烷（氯二甲基硅烷（ClSiHMe2）、二氯甲基硅烷（Cl2SiHMe）、三氯硅烷（Cl3SiH））之间的反应展开了探究。Cp*(R3P)Ru(H)3与氯二甲基硅烷（ClSiHMe2）的反应在90 ℃下进行，可生成两类产物：Cp*(R3P)Ru(H)2(SiClMe2)（记为1）与Cp*(R3P)Ru(H)2(SiCl2Me)（记为2）。配合物2的产率随膦配体空间位阻的减小而升高。对Cp*(Pri3P)Ru(H)2(SiClMe2)（1a）与Cp*(Pri2MeP)Ru(H)2(SiClMe2)（1b）的X射线单晶衍射结构分析结果证实，其存在配体间超价相互作用Ru−H···Si−Cl。通过Cp*(R3P)Ru(H)3与二氯甲基硅烷（Cl2SiHMe）在60 ℃下的反应，可制备得到化合物Cp*(R3P)Ru(H)(Cl)(SiCl2Me)（3），并通过核磁共振（NMR）与红外（IR）光谱对其完成表征。配合物Cp*(Pri3P)Ru(Cl)(SiCl2Me)(H)（3a）与过量三甲基膦（PMe3）反应，可发生H−Si消除反应，生成产物Cp*(PMe3)2RuCl。在三乙胺（NEt3）存在下，Cp*(R3P)Ru(H)3（R3P分别为三异丙基膦（Pri3P）、异丙基二甲基膦（Pri2MeP））与二氯甲基硅烷（Cl2SiHMe）在90 ℃下反应，可生成二氢硅基化合物Cp*(R3P)Ru(H)2(SiCl2Me)（其中R3P=Pri3P时为2a，R3P=Pri2MeP时为2b）。此类产物的X射线衍射结构可被合理阐释为存在双配体间超价相互作用Ru−H2···Si−Cl2。在100 ℃下，Cp*(MePri2P)Ru(H)3与过量三氯甲基硅烷（Cl3SiMe）之间的核磁共振监测反应，可高选择性地生成Cp*(MePri2P)Ru(H)(Cl)(SiCl2Me)。配合物Cp*(R3P)Ru(Cl)(SiCl3)(H)（5）可通过Cp*(R3P)Ru(H)3与三氯硅烷（Cl3SiH）在室温下的反应制备得到，并通过核磁共振（NMR）与红外（IR）光谱完成表征。在三乙胺（NEt3）存在下，Cp*(R3P)Ru(H)3（R3P分别为三异丙基膦（Pri3P）、异丙基二甲基膦（Pri2MeP））与三氯硅烷（Cl3SiH）在60 ℃下反应，可生成二氢硅基化合物Cp*(R3P)Ru(H)2(SiCl2H)（R3P=Pri3P时为6a，R3P=Pri2MeP时为6b），同时伴随少量其他副产物混合物；而在二异丙基乙胺（NPri2Et）存在下进行的同类反应，则可生成二氢硅基化合物Cp*(R3P)Ru(H)2(SiClH2)（R3P=Pri3P时为7a，R3P=Pri2MeP时为7b）。通过氢化铝锂（LiAlH4）还原Cp*(Pri3P)Ru(Cl)(SiCl3)(H)（5a）制备得到的配合物Cp*(Pri3P)RuH2(SiH3)（8a），可与二甲基苯胺盐酸盐（[NHMe2Ph]Cl）反应，生成Cp*(Pri3P)Ru(H)3与Cp*(Pri3P)Ru(H)2(SiClH2)（7a）的混合物。已通过X射线单晶衍射结构分析，测定了1a、1b、2a、2c、5b、5c、5d以及8a的晶体结构。