328947-17-7Relevant academic research and scientific papers
R-Group reversal of isomer stability for RuH(X)L2(CCHR) vs. Ru(X)L2(CCH2R): Access to four-coordinate ruthenium carbenes and carbynes
Coalter III,Bollinger,Eisenstein,Caulton
, p. 925 - 927 (2000)
NaOPh converts equimolar RuHClL2(=C=CHR) (L=PPr3/i and PCy3) first to RuH(OPh)L2(=C=CHR), but then, only for R = H, these isomerize to the more stable carbynes Ru(OPh)L2(C-CH3); the rate of isomerization is slowed considerably by THF. RuH(OPh)L2(=C=CHR) can also be synthesized by reaction of RuCl2L2[=CH(CH2R)] with 2 NaOPh; again, only when R = H does the hydrido vinylidene isomerize to the carbyne. While phenoxide converts RuCl2L2(=CHPh) to Ru(OPh)L2(CPh), via the observable intermediates RuCl2-n(OPh)nL2(=CHPh), alkoxides OBui and OAdamantyl cause phosphine displacement to give the four-coordinate carbenes Ru(OR)2L(=CHPh). DFT (B3PW91) calculations show these d6 species have a traditional cis-divacant octahedral structure with trans OR groups.
