Hess Gisela D, Fiedler Tobias, Hampel Frank, Gladysz John A
Institut für Organische Chemie and Interdisciplinary Center for Molecular Materials, Friedrich-Alexander-Universität Erlangen-Nürnberg , Henkestraße 42, 91054 Erlangen, Germany.
Department of Chemistry, Texas A&M University , PO Box 30012, College Station, Texas 77842-3012, United States.
Inorg Chem. 2017 Jul 3;56(13):7454-7469. doi: 10.1021/acs.inorgchem.7b00909. Epub 2017 Jun 9.
Reactions of Re(CO)(X) (X = Cl, Br) or [Re(CO)(NO)(μ-Cl)(Cl)] and the phosphines P((CH)CH═CH) (m = 6, a; 7, b; 8, c) give mer,trans-Re(CO)(X)(P((CH)CH═CH)) (53-95%) or cis,trans-Re(CO) (NO) (Cl)(P((CH)CH═CH)) (57%), respectively. Additions of Grubbs' catalyst (5-10 mol %, 0.0010-0.0012 M) and subsequent hydrogenations (PtO, ≤5 bar) yield the gyroscope-like complexes mer,trans-R e(CO)(X)(P((CH)) P) (n = 2m + 2; X = Cl, 7a,c; Br, 8a,c; 18-61%) or cis,trans-R e(CO)(NO)(Cl)(P((CH)) P) (14%), respectively, and/or the isomers mer,trans-R e(CO)(X)( P(CH) CH)((CH))( P(CH) CH) (X = Cl, 7'a-c; Br, 8'b; 6-27%). The latter are derived from a combination of interligand and intraligand metatheses. Reactions of 7a or 8a with NaI, PhZn, or MeLi give mer,trans-R e(CO)(X)(P((CH)) P) (X = I, 11a; Ph, 12a; Me, 13a; 34-87%). The C NMR spectra of 7a-c, 8a-c, 11a, and 13a show rotation of the Re(CO)(X) moieties to be fast on the NMR time scale at room temperature (and at -90 °C for 8a). In contrast, the phenyl group in 12a acts as a brake, and two sets of C NMR signals (2:1) are observed for the methylene chains. The crystal structures of 7a, 8a, 12a, and 13a are analyzed with respect to Re(CO)(X) rotation in solution and the solid state.
铼化合物Re(CO)(X)（X = Cl、Br）或[Re(CO)(NO)(μ-Cl)(Cl)]与膦P((CH)CH═CH)（m = 6，a；7，b；8，c）反应，分别生成mer,trans-Re(CO)(X)(P((CH)CH═CH))（产率53 - 95%）或cis,trans-Re(CO)(NO)(Cl)(P((CH)CH═CH))（产率57%）。加入格拉布催化剂（5 - 10 mol%，0.0010 - 0.0012 M）并随后进行氢化反应（PtO，≤5 bar），分别生成类似陀螺仪的配合物mer,trans-Re(CO)(X)(P((CH))P)（n = 2m + 2；X = Cl，7a,c；Br，8a,c；产率18 - 61%）或cis,trans-Re(CO)(NO)(Cl)(P((CH))P)（产率14%），和/或异构体mer,trans-Re(CO)(X)(P(CH)CH)((CH))(P(CH)CH)（X = Cl，7'a - c；Br，8'b；产率6 - 27%）。后者源自配体间和配体内复分解反应的组合。7a或8a与NaI、PhZn或MeLi反应生成mer,trans-Re(CO)(X)(P((CH))P)（X = I，11a；Ph，12a；Me，13a；产率34 - 87%）。7a - c、8a - c、11a和13a的碳核磁共振谱表明，在室温下（对于8a在 - 90 °C时），Re(CO)(X)部分在核磁共振时间尺度上旋转很快。相比之下，12a中的苯基起到了阻碍作用，对于亚甲基链观察到两组碳核磁共振信号（比例为2:1）。针对溶液和固态中Re(CO)(X)的旋转对7a、8a、12a和13a的晶体结构进行了分析。
