Octahedral Gyroscope-like Molecules Consisting of Rhenium Rotators within Cage-like Dibridgehead Diphosphine Stators: Syntheses, Substitution Reactions, Structures, and Dynamic Properties
作者:Gisela D. Hess、Tobias Fiedler、Frank Hampel、John A. Gladysz
DOI:10.1021/acs.inorgchem.7b00909
日期:2017.7.3
Reactions of Re(CO)5(X) (X = Cl, Br) or [Re2(CO)4(NO)2(μ-Cl)2(Cl)2] and the phosphines P((CH2)mCH═CH2)3 (m = 6, a; 7, b; 8, c) give mer,trans-Re(CO)3(X)(P((CH2)mCH═CH2)3)2 (53–95%) or cis,trans-Re(CO) (NO) (Cl)2(P((CH2)6CH═CH2)3)2 (57%), respectively. Additions of Grubbs’ catalyst (5–10 mol %, 0.0010–0.0012 M) and subsequent hydrogenations (PtO2, ≤5 bar) yield the gyroscope-like complexes mer,tran
Re(CO)5(X)(X = Cl,Br)或[Re 2(CO)4(NO)2(μ-Cl)2(Cl)2 ]与膦P((CH 2)m的反应CH = CH 2)3(米= 6,一个; 7,b 8,ç)给出聚体,反式-Re(CO)3(X)(P((CH 2)米CH = CH 2)3)2(53–95%)或顺式,反式-Re(CO)(NO)(Cl)2(P((CH 2)6 CH = CH 2)3)2(57%)。添加Grubbs催化剂(5-10 mol%,0.0010-0.0012 M)和随后的氢化反应(PtO 2,≤5bar )得到陀螺仪状配合物mer,trans -R e(CO)3(X)(P( (CH 2)n)3 P)(n = 2 m + 2; X = Cl,7a,c ; Br,8a,c ; 18-61%)或顺式,反式-R e(CO)(NO)( Cl)2(P((CH 2)14)3P)(14%)和/或异构体mer,trans