Different coordination modes of an aryl-substituted hydrotris(pyrazolyl) borate ligand in rhodium and iridium complexes

Content Provider	Semantic Scholar
Author	Conejero, Salvador Esqueda, Ana C. Valpuesta, José E. V. Álvarez, Eleuterio Maya, Celia Carmona, Ernesto
Copyright Year	2011
Abstract	Complexes Tp tol Rh(C 2 H 4 ) 2 ( 1a ) and Tp tol Rh(CH 2 C(Me)C(Me) CH 2 ) ( 1b ) have been prepared by reaction of KTp tol with the appropriate [RhCl(olefin) 2 ] 2 dimer (Tp tol means hydrotris(3- p -tolylpyrazol-1-yl)borate). The two complexes show a dynamic behaviour that involves exchange between κ 2 and κ 3 coordination modes of the Tp tol ligand. The iridium analogue, Tp tol Ir(CH 2 C(Me)CH CH 2 ) ( 2 ) has also been synthesized, and has been converted into the Ir(III) dinitrogen complex [( κ 4 -N , N ', N '', C -Tp tol )Ir(Ph)(N 2 ) ( 3 ) by irradiation with UV light under a dinitrogen atmosphere. Compound 3 constitutes a rare example of Ir(III)–N 2 complex structurally characterized by X-ray crystallography. Its N 2 ligand can be easily substituted by acetonitrile or ethylene upon heating and denticity changes in the Tp tol ligand, from κ 4 -N , N ', N '', C (monometallated Tp tol , from now on represented as Tp tol′ ) to κ 5 -N , N′ , N″ , C , C″ (dimetallated Tp tol ligand, represented as Tp tol ″ ) have been observed. When complex 3 is heated in the presence of acetylene, dimerization of the alkyne takes place to yield the enyne complex [( κ 5 -N , N′ , N′′ , C , C′ -Tp tol )Ir(CH 2 CHC CH), 7 ¸ in which the unsaturated organic moiety is bonded to iridium through the carbon–carbon double bond.
Starting Page	165
Ending Page	172
Page Count	8
File Format	PDF HTM / HTML
DOI	10.1016/j.ica.2010.12.031
Volume Number	369
Alternate Webpage(s)	https://idus.us.es/xmlui/bitstream/handle/11441/87933/Different%20Coordination%20Modes%20.pdf?isAllowed=y&sequence=1
Alternate Webpage(s)	https://doi.org/10.1016/j.ica.2010.12.031
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article