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Synthesis and reactions of group 4 imido complexes supported by cyclooctatetraene ligands

机译：环辛酸酯烯配体负载的4族亚氨基配合物的合成和反应

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摘要

The reactions of the pseudo-two-coordinate titanium imido complexes [Ti((NBu)-Bu-t)(COT)] (1) (COT = eta(8)-C8H8), [Ti((NBu)-Bu-t)(COT")] (2) (COT" = eta(8)-1,4-C8H6(SiMe3)(2)), and [Ti(NAr)(COT)] (3) (Ar = 2,6-(Pr2C6H3)-Pr-i) with a variety of organic substrates are reported. Reaction of 1 with CO2, (BuNCO)-Bu-t, or ArNCO and reaction of 3 with CO2 or (BuNCO)-Bu-t afforded the organic products (BuNCO)-Bu-t, (BuNCNBu)-Bu-t-Bu-t, (BuNCNAr)-Bu-t, ArNCO, and (ArNCNBu)-Bu-t, respectively, and a titanium oxo species. These reactions proceeded via an initial [2 + 2] cycloaddition to form an N,O-bound intermediate of the type [Ti{N(R)C(O)R'}(COT)], which subsequently underwent a retrocycloaddition to give an organic product and the titanium oxo species. In contrast, reaction of 3 with ArNCO led to the formation of the N,N-bound [2 + 2] cycloaddition product [Ti{N(Ar)C(O)N(Ar)}(COT)] (7), In general, the reactions of 1 and 3 with CS2 and isothiocyanates also resulted in an initial [2 + 2] cycloaddition to form an N,S-bound intermediate of the type [Ti{N(R)C(S)R'}(COT)], which also subsequently underwent a retrocycloaddition to give an organic product and a metal sulfide species. However, the N,S-bound compound [Ti{N(Ar)C(S)S}(COT)] (10) was stable to retrocycloaddition and was isolated. Proton transfer reactions occurred between pinacol and compounds 1-3 to form the bis(alkoxide) species [Ti{OC(Me)(2)C(Me)(2)O}(COT)] (11) (from 1 or 3) or [Ti{OC(Me)(2)C(Me)(2)O} (COT")] (12) (from 2) and the corresponding free amine. The reactions between 1-3 and 2 equiv of the thiols (BuSH)-Bu-t and HS-2,4,6-(Pr3C6H2)-Pr-i all resulted in the oxidation of the thiol to the disulfides (BuS)-Bu-t-(SBu)-Bu-t and (2,4,6-(Pr3C6H2)-Pr-i)S-S(2,4,6-(Pr3C6H2)-Pr-i). Treatment of 1 with (BuNC)-Bu-t in the presence of 1,3,5,7-cyclooctatetraene led to formal nitrene group transfer and the formation of the Ti(II) species [Ti(COT)(eta(4)-C8H8)] (13) and (BuNCNBu)-Bu-t-Bu-t. The analogous reactions between 2 and 3 and (BuNC)-Bu-t resulted in the formation of the adducts [Ti((NBu)-Bu-t)(COT")((CNBu)-Bu-t)] (15) and [Ti(NAr)(COT)((CNBu)-Bu-t)] (17), and similarly the reaction between 1 and pyridine led to the isolation of the adduct [Ti((NBu)-Bu-t)-(COT)(py)] (19) (py = pyridine). Complex 19 was crystallographically characterized. DFT studies indicated that the interaction between pyridine and the Ti center in 19 and (BuNC)-Bu-t and the Ti center in 17 was electrostatic in nature. Complexes of the type [Ti(NR)(COT)(AlMe3-xClx)] (R = Bu-t, x = 0 (20); R = Ar, x = 0 (21); R = Bu-t, x = 1 (22); R = Ar, x = 1 (23)) were formed through the reactions of 1 and 3 with AlMe3 and AlMe2Cl, and DFT studies indicated that they contained four-membered metallacyclic rings, Attempts to prepare monomeric zirconium imido cyclooctatetraene complexes through the reactions of [Zr-2(mu-NR)(2)Cl-4(THF)(x)] (R = Bu-t, x = 3; R = 2,6-Me2C6H3(Ar'), x = 4) with K2COT, Li2COT"center dot 1.
机译：准二配位钛亚氨基络合物[Ti（（NBu）-Bu-t）（COT）]（1）（COT = eta（8）-C8H8），[Ti（（NBu）-Bu- t）（COT“）]（2）（COT” = eta（8）-1,4-C8H6（SiMe3）（2））和[Ti（NAr）（COT）]（3）（Ar = 2报道了具有多种有机底物的6-（Pr 2 C 6 H 3）-Pr-i）。 1与CO2，（BuNCO）-Bu-t或ArNCO的反应以及3与CO2或（BuNCO）-Bu-t的反应得到有机产物（BuNCO）-Bu-t，（BuNCNBu）-Bu-t- Bu-t，（BuNCNAr）-Bu-t，ArNCO和（ArNCNBu）-Bu-t，以及钛氧基。这些反应通过初始的[2 + 2]环加成反应进行，形成[Ti {N（R）C（O）R'}（COT）]类型的N，O结合中间体，随后进行逆向加成反应得到有机产品和钛氧基。相反，3与ArNCO的反应导致形成N，N结合的[2 + 2]环加成产物[Ti {N（Ar）C（O）N（Ar）}（COT）]（7），通常，1和3与CS2和异硫氰酸酯的反应还导致初始[2 + 2]环加成反应，形成[Ti {N（R）C（S）R'}类型的N，S结合中间体（COT）]，随后还进行了环加成反应，得到有机产物和金属硫化物。但是，N，S结合的化合物[Ti {N（Ar）C（S）S}（COT）]（10）对逆环加成稳定并已分离。频哪醇和化合物1-3之间发生质子转移反应以形成双（醇盐）物种[Ti {OC（Me）（2）C（Me）（2）O}（COT）]（11）（从1或3 ）或[Ti {OC（Me）（2）C（Me）（2）O}（COT“）]（12）（来自2）和相应的游离胺。1-3至2当量的硫醇（BuSH）-Bu-t和HS-2,4,6-（Pr3C6H2）-Pr-i均导致硫醇氧化为二硫化物（BuS）-Bu-t-（SBu）-Bu-t和（2,4,6-（Pr3C6H2）-Pr-i）SS（2,4,6-（Pr3C6H2）-Pr-i）。在存在1的情况下，用（BuNC）-Bu-t处理1 3,5,7-环辛酸酯导致正式的腈基转移并形成Ti（II）物种[Ti（COT）（eta（4）-C8H8）]（13）和（BuNCNBu）-Bu-t-Bu -t。2和3与（BuNC）-Bu-t之间的类似反应导致形成加合物[Ti（（NBu）-Bu-t）（COT“）（（CNBu）-Bu-t）] （15）和[Ti（NAr）（COT）（（CNBu）-Bu-t）]（17），类似地，1与吡啶之间的反应导致加合物[Ti（（NBu）-Bu-t- t）-（COT）（py）]（19）（py =吡啶）。配合物19通过晶体学表征。 DFT研究表明，吡啶与19中的Ti中心以及（BuNC）-Bu-t与17中的Ti中心之间的相互作用本质上是静电的。 [Ti（NR）（COT）（AlMe3-xClx）]类型的络合物（R = Bu-t，x = 0（20）; R = Ar，x = 0（21）; R = Bu-t，x = 1（22）; R = Ar，x = 1（23））是通过1和3与AlMe3和AlMe2Cl的反应形成的，并且DFT研究表明它们包含四元金属环，试图制备单体锆亚氨基通过[Zr-2（mu-NR）（2）Cl-4（THF）（x）]的反应生成环辛酸酯络合物（R = Bu-t，x = 3; R = 2,6-Me2C6H3（Ar'） ，x = 4），带有K2COT，Li2COT“中心点1。

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