Syntheses, Structures, and Thermal Properties of Gyroscope-like Complexes Consisting of PtCl2 Rotators Encased in Macrocyclic Dibridgehead Diphosphines P((CH2)n)3P with Extended Methylene Chains (n=20/22/30) and Isomers Thereof

Reactions of P((CH2)(m)CH=CH2)(3) (2.0 equiv; m = 9 (f), 10 (g), 14 (k)) and PtCl2 in toluene give trans-PtCl2(P((CH2),CH=CH2)(3))(2) (trans-1f,g,k; 63-49%). Reactions of trans-lf,g with Grubbs first generation catalyst (CH2Cl2/reflux) followed by hydrogenations (cat. PtO2) afford chromatographically separable gyroscope-like trans-(GRAPHICS) (trans-2f,g, 3-19%; from interligand metathesis) and trans-(GRAPHICS) (trans-2'f,g, 25-12%; from inter and intraligand metathesis), where n = 2m + 2. Under analogous conditions, trans-1k gives only cis-(GRAPHICS) (cis-2k, 39%), but when o-C6H4CL2 solutions are kept at 180 C, trans-2k forms (quantitative by P-31 NMR; 72% isolated). In contrast, a similar sequence with the Hoveyda-Grubbs second generation catalyst gives only trans-2k (8%). The stability order cis > trans is established for lg and 2'f,g in CH2Cl2 (61-56:39-44; months at RT), but the opposite is found for lg and 2'f in toluene (9-7:91-93) or 2'f in o-C6H4Cl2 (7:93). Thus, it is proposed that the conversion of trans-lk to cis-2k involves a geometrical isomerization of the educt or an intermediate catalyzed by a species derived from Grubbs catalyst. The crystal structures of trans-2gTHF and cis-2'f,g are determined and analyzed in detail.