Activation of H₂ over the Ru−Zn Bond in the Transition Metal−Lewis Acid Heterobimetallic Species [Ru(IPr)₂(CO)ZnEt]⁺

Abstract

Through a dramatic advance in the coordination chemistry of the zinc-hydride bond, we describe the trajectory for the approach of this bond to transition metals. The dynamic reaction coordinate was interrogated through analysis of a series of solid state structures and is one in which the TM-H-Zn angle becomes increasingly acute as the TM-Zn distance decreases. Parallels may be drawn with the oxidative addition of boron-hydrogen and silicon-hydrogen bonds to transition metal centers.

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

“…4 ]. [375] [374] Furthermore,t he reaction of [Ru(IPr) 2 (CO)H] + with Et 2 Zn proceeds via alkane elimination to yield [Ru(IPr) 2 -(CO)ZnEt] + ,w hich features an unusual unsupported RuÀ Zn bond, across which dihydrogen can be activated to form the dihydrogen dihydride complex [Ru(IPr) 2 (CO)( h 2 -H 2 )-(H 2 )ZnEt] + .…”

Trajectory of Approach of a Zinc–Hydrogen Bond to Transition Metals

“…[5] The proposition that these species could dimerize by 3-center 2-electron bonds seeded ideas that ultimately led to the discovery of dihydrogen complexes. [6] A handful of heterobimetallic complexes containing transition metal and zinc centers bridged by hydride ligands are known, [7][8][9][10][11][12][13][14] The majority however, include more than one bridging hydride ligand clouding analysis of the TM-H-Zn group. Through kinetic protection of a zinc center with a sterically demanding ligand, we recently isolated a rare example of a heterobimetallic complex possessing an unsupported Cu-H-Zn moiety.…”

“…[6] Ah andful of heterobimetallic complexes containing transition metal and zinc centers bridged by hydride ligands are known. [7][8][9][10][11][12][13][14][15] Themajority however, include more than one bridging hydride ligand clouding analysis of the TM-H-Zn group.T hrough kinetic protection of az inc center with asterically demanding ligand, we recently isolated ar are example of ah eterobimetallic complex possessing an unsupported Cu-H-Zn moiety. [15c] Here we describe an advance in the coordination chemistry of the zinc-hydride bond to transition metals.Through analysis of aseries of solid state structures and calculations,w ed escribe the reaction trajectory for the approach of as ingle zinc-hydride bond to atransition metal.…”

“…The fsr of this series of 1.02-1.04, however, is smaller than that observed in 2a-c.I n3a,b both short Zn-CO distances [3a,2.423(3) ; 3b,2.548(3)] and the deviation of the M-C-O angle from 1808 8 are consistent with the formation of semi-bridging carbonyl ligands.I nfrared spectroscopy supports the formulation and n(CO) peaks may be assigned to terminal (3a,1 905 cm À1 ; 3b,1 937 cm À1 )a nd semi-bridging carbonyls (3a,1799 cm À1 ; 3b,1852 cm À1 ). [19] In 3a,b only as ingle 13 Table S1 in the Supporting Information). The latter s-complexes have been described as having little or no back-bonding to the HÀEb ond from the transition metal center and based on infrared spectroscopy it appears 3b is no different.…”

Well‐Defined Heterobimetallic Reactivity at Unsupported Ruthenium–Indium Bonds

“…An alternative approachi st os trip away the scaffold to leave two coordinatively unsaturated metals held together by an "unsupported" bond. [10] This readily adds H 2 across the RuÀZn bond to give 3.D FT calculations showed that the Zn centre acts as ar eversibleh ydride acceptor that participates directly in bond cleavage. [10] This readily adds H 2 across the RuÀZn bond to give 3.D FT calculations showed that the Zn centre acts as ar eversibleh ydride acceptor that participates directly in bond cleavage.…”