Widemann Max, Jeggle Sebastian, Auer Maximilian, Eichele Klaus, Schubert Hartmut, Sindlinger Christian P, Wesemann Lars
Institut für Anorganische Chemie Auf der Morgenstelle 18 72076 Tübingen Germany
Institut für Anorganische Chemie, RWTH Aachen University Landoltweg 1a D-52074 Aachen Germany
Chem Sci. 2022 Feb 22;13(14):3999-4009. doi: 10.1039/d2sc00297c. eCollection 2022 Apr 6.
In a reaction of tantalocene trihydride with the low valent aryl tin cation [ArSn(CH)][Al(OC{CF})] (1a) the hydridostannylene complex [CpTaH-Sn(H)Ar][Al(OC{CF})] (2) was synthesized. Hydride bridged adducts [CpWHEAr*][Al(OC{CF})] (E = Sn 3a, Pb 3b) were isolated as products of the reaction between CpWH and cations [ArE(CH)][Al(OC{CF})] (E = Sn 1a, Pb 1b). The tin adduct 3a exhibits a proton migration to give the hydridostannylene complex [CpW(H)[double bond, length as m-dash]Sn(H)Ar][Al(OC{CF})] 4a. The cationic complex 4a is deprotonated at the tin atom in reaction with base NHC at 80 °C to give a hydrido-tungstenostannylene [CpW(H)SnAr*] 5a. Reprotonation of metallostannylene 5a with acid [H(EtO)][BAr] provides an alternative route to hydridotetrylene coordination. Complex 4a adds hydride to give the dihydrostannyl complex [CpW(H)-SnHAr*] (7). With styrene 4a shows formation of a hydrostannylation product [CpW(H)[double bond, length as m-dash]Sn(CHCHPh)Ar*][Al(OC{CF})] (8). The lead adduct 3b was deprotonated with NHC to give plumbylene 5b [CpW(H)PbAr*]. Protonation of 5b with [H(EtO)][Al(OC{CF})] at -40 °C followed by low temperature NMR spectroscopy indicates a hydridoplumbylene intermediate [CpW(H)[double bond, length as m-dash]Pb(H)Ar*] (4b). Hydrido-tungstenotetrylenes of elements Ge (5c), Sn (5a) and Pb (5b) were also synthesized reacting the salt [CpW(H)Li] with organotetrylene halides. The metallogermylene [CpW(H)GeAr*] (5c) shows an isomerization 1,2-H-migration to give the hydridogermylene [CpW[double bond, length as m-dash]Ge(H)Ar*] (9), which is accelerated by addition of AIBN. 9 is at rt photochemically transferred back to 5c under light of a mercury vapor lamp. Zirconocene dihydride [CpZrH] reacts with tin cation 1a to give the trinuclear hydridostannylene adduct 10 [({CpZr}{μ-H})(μ-H)μ-Sn(H)Ar*][Al(OC{CF})]. Deprotonation of 10 was carried out using benzyl potassium to give neutral [({CpZr}{μ-H})(μ-H)μ-Sn(H)Ar*] (11). 11 was also obtained from the reaction of low valent tin hydride [ArSnH] with two equivalents of [CpZrH]. The trihydride ArSnH reacts with half of an equivalent of [CpZrH] under evolution of hydrogen and formation of a dihydrostannyl complex 13 [CpZr(μ-H)SnHAr*] and with further equivalents of ArSnH to give bis(hydridostannylene) complex [CpZr{Sn(H)Ar}].
在三氢化二茂钽与低价芳基锡阳离子[ArSn(CH)][Al(OC{CF})]（1a）的反应中，合成了氢化亚锡烯配合物[CpTaH-Sn(H)Ar][Al(OC{CF})]（2）。氢化桥连加合物[CpWHEAr*][Al(OC{CF})]（E = Sn 3a，Pb 3b）是CpWH与阳离子[ArE(CH)][Al(OC{CF})]（E = Sn 1a，Pb 1b）反应的产物。锡加合物3a发生质子迁移，生成氢化亚锡烯配合物[CpW(H)[双键，长度如m破折号]Sn(H)Ar][Al(OC{CF})] 4a。阳离子配合物4a在80℃与碱NHC反应时，在锡原子处去质子化，生成氢化钨亚锡烯[CpW(H)SnAr*] 5a。用酸[H(EtO)][BAr]对金属亚锡烯5a进行再质子化，提供了一条通往氢化四价烯配位的替代途径。配合物4a加成氢化物，生成二氢锡基配合物[CpW(H)-SnHAr*]（7）。与苯乙烯反应时，4a显示形成了氢锡化产物[CpW(H)[双键，长度如m破折号]Sn(CHCHPh)Ar*][Al(OC{CF})]（8）。铅加合物3b用NHC去质子化，生成铅烯5b [CpW(H)PbAr*]。在-40℃用[H(EtO)][Al(OC{CF})]对5b进行质子化，随后进行低温核磁共振光谱分析，表明存在氢化铅烯中间体[CpW(H)[双键，长度如m破折号]Pb(H)Ar*]（4b）。元素Ge（5c）、Sn（5a）和Pb（5b）的氢化钨四价烯也是通过盐[CpW(H)Li]与有机四价烯卤化物反应合成的。金属亚锗烯[CpW(H)GeAr*]（5c）发生1,2 - H迁移异构化，生成氢化锗烯[CpW[双键，长度如m破折号]Ge(H)Ar*]（9），加入AIBN可加速此过程。在室温下，9在汞蒸气灯的光照下光化学转化回5c。二氢化二茂锆[CpZrH]与锡阳离子1a反应，生成三核氢化亚锡烯加合物10 [({CpZr}{μ-H})(μ-H)μ-Sn(H)Ar*][Al(OC{CF})]。用苄基钾对10进行去质子化，得到中性的[({CpZr}{μ-H})(μ-H)μ-Sn(H)Ar*]（11）。11也可由低价氢化锡[ArSnH]与两当量的[CpZrH]反应得到。三氢化物ArSnH与半当量的[CpZrH]反应，在氢气放出的情况下生成二氢锡基配合物13 [CpZr(μ-H)SnHAr*]，并与更多当量的ArSnH反应，生成双（氢化亚锡烯）配合物[CpZr{Sn(H)Ar}]。
