Adams Richard D, Kaushal Meenal, Rassolov Vitaly A, Smith Mark D
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States.
Inorg Chem. 2022 Aug 8;61(31):12262-12274. doi: 10.1021/acs.inorgchem.2c01471. Epub 2022 Jul 27.
New zwitterionic dirhenium carbonyl complexes containing ammonioethenyl and phosphonioethenyl ligands have been synthesized and studied. The reaction of Re(CO) with CH and MeNO yielded the dirhenium complex Re(CO)(NMe) () and the new zwitterionic complex Re(CO)[η--2-CH═CH(NMe)] (). Compound was characterized structurally and was found to have a NMe ligand in an equatorial coordination site to a long Re-Re single bond, Re-Re = 3.0938(2) Å. Compound can be obtained from the reaction of with ethyne (CH) formally by the insertion of ethyne into the Re-N bond to the NMe ligand. Compound contains a 2-trimethylammonioethenyl ligand, CH═CH(NMe), that is formally a zwitterion having a positive charge on the nitrogen atom and a negative charge on the terminal carbon atom. When coordinated to rhenium by the terminal ethenyl carbon atom, the negative charge on the CH═CH(NMe) carbon atom is formally transferred to the rhenium atom. The reaction of Re(CO) with CH and NEt in the presence of MeNO yielded the new dirhenium complex Re(CO)[η--2-CH═CH(NEt)] () together with some and . Compound is structurally similar to , but it contains a NEt group in the ammonioethenyl ligand in the place of the NMe group in . Reactions of with PMePh and PPh yielded the zwitterionic 2-arylphosphonioethenyl-coordinated dirhenium carbonyl complexes, Re(CO)[η--2-CH═CH(PPhMe)] () and Re(CO)[η--2-CH═CH(PPh)] (), and the zwitterionic 1-phosphonioethenyl ligand in the dirhenium carbonyl complexes, Re(CO)[η-1-C(PPhMe)(═CH)] (), Re(CO)[μ-η-1-C(PPhMe)(═CH)] (), and Re(CO)[[μ-η-1-C(PPh)(CH)] (). Compound was converted to and the new compound Re(CO)(μ-H)[μ-η-1-(CHC)P(Ph)(Me)(-CH)], () by decarbonylation using MeNO. Compound contains an -metalated phenyl ring. The new products , , , , , and were characterized structurally by single-crystal X-ray diffraction analyses.
已合成并研究了含有氨乙基和膦乙基配体的新型两性离子二铼羰基配合物。Re(CO)与CH和MeNO的反应生成了二铼配合物Re(CO)(NMe) ()和新型两性离子配合物Re(CO)[η--2-CH═CH(NMe)] ()。对化合物 进行了结构表征，发现其在赤道配位位点有一个NMe配体与一个长的Re-Re单键相连，Re-Re = 3.0938(2) Å。化合物 可通过乙炔(CH)与 的反应，使乙炔正式插入到NMe配体的Re-N键中得到。化合物 含有一个2-三甲基铵乙烯基配体CH═CH(NMe)，它正式是一个两性离子，氮原子带正电荷，末端碳原子带负电荷。当通过末端乙烯基碳原子与铼配位时，CH═CH(NMe)碳原子上的负电荷正式转移到铼原子上。Re(CO)与CH和NEt在MeNO存在下的反应生成了新型二铼配合物Re(CO)[η--2-CH═CH(NEt)] ()以及一些 和 。化合物 与 在结构上相似，但它在氨乙基配体中含有一个NEt基团，取代了 中的NMe基团。 与PMePh和PPh的反应生成了两性离子的2-芳基膦乙基配位的二铼羰基配合物Re(CO)[η--2-CH═CH(PPhMe)] ()和Re(CO)[η--2-CH═CH(PPh)] ()，以及二铼羰基配合物中的两性离子1-膦乙基配体Re(CO)[η-1-C(PPhMe)(═CH)] ()、Re(CO)[μ-η-1-C(PPhMe)(═CH)] ()和Re(CO)[[μ-η-1-C(PPh)(CH)] ()。化合物 通过使用MeNO脱羰基转化为 和新化合物Re(CO)(μ-H)[μ-η-1-(CHC)P(Ph)(Me)(-CH)] ()。化合物 含有一个 -金属化苯环。通过单晶X射线衍射分析对新产物 、 、 、 、 、 和 进行了结构表征。
