Issue 12, 2000

R-Group reversal of isomer stability for RuH(X)L2(CCHR) [italic v (to differentiate from Times ital nu)]s. Ru(X)L2(CCH2R): access to four-coordinate ruthenium carbenes and carbynes

Abstract

NaOPh converts equimolar RuHClL2([double bond, length half m-dash]C[double bond, length half m-dash]CHR) (L = PPr3i and PCy3) first to RuH(OPh)L2([double bond, length half m-dash]C[double bond, length half m-dash]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([double bond, length half m-dash]C[double bond, length half m-dash]CHR) can also be synthesized by reaction of RuCl2L2[[double bond, length half m-dash]CH(CH2R)] with 2 NaOPh; again, only when R = H does the hydrido vinylidene isomerize to the carbyne. While phenoxide converts RuCl2L2([double bond, length half m-dash]CHPh) to Ru(OPh)L2(CPh), [italic v (to differentiate from Times ital nu)]ia the observable intermediates RuCl2−n(OPh)nL2([double bond, length half m-dash]CHPh), alkoxides OBut and OAdamantyl cause phosphine displacement to give the four-coordinate carbenes Ru(OR)2L([double bond, length half m-dash]CHPh). DFT (B3PW91) calculations show these d6 species have a traditional cis-divacant octahedral structure with trans OR groups.

Supplementary files

Article information

Article type
Letter
Submitted
23 Aug 2000
Accepted
15 Sep 2000
First published
06 Nov 2000

New J. Chem., 2000,24, 925-927

R-Group reversal of isomer stability for RuH(X)L2(CCHR) [italic v (to differentiate from Times ital nu)]s. Ru(X)L2(CCH2R): access to four-coordinate ruthenium carbenes and carbynes

J. N. Coalter, III, J. C. Bollinger, O. Eisenstein and K. G. Caulton, New J. Chem., 2000, 24, 925 DOI: 10.1039/B006971J

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