Addition of aluminium, zinc and magnesium hydrides to rhodium(iii)

Abstract

We report the addition of M–H bonds (M = Al, Zn, Mg) to a Rh(iii) intermediate generated from the reductive elimination of triethylsilane from [Cp*Rh(H)2(SiEt3)2].

Stereoisomerism of bis(σ‐Zincane) Complexes: Evidence for an Intramolecular Pathway

“…In the past few years, we, and others, have investigated the coordination of Al−H, Ga−H, Zn−H and Mg−H bonds to transition metals . Here, we report stereoisomerism in bis(σ‐zincane) complexes of the Group 6 carbonyls: fluxional heterotrimetallics.…”

“…[27][28][29] Insight into isomerisation mechanismsm ay have direct relevancet oc atalytic processesi nvolving s-complex-assisted metathesis, [10,30] for which dynamicp rocesses involving EÀHb onds adjacent to reactive hydrides are well understood. [31,32] In the past few years, we, [33][34][35][36][37][38] and others, [39][40][41][42][43] have investigated the coordination of AlÀH, GaÀH, ZnÀHa nd MgÀHb onds to transition metals. [44,45] Here, we report stereoisomerism in bis(s-zincane) complexes of the Group 6c arbonyls:f luxional heterotrimetallics.…”

Tunable Binding of Dinitrogen to a Series of Heterobimetallic Hydride Complexes

“…For comparison, in 2015 we reported a series of rhodium hydride complexes which possess similar fsr to those reported herein but with defined Rh-M bonds. 23 The metal-metal bonding was supported by both calculations and spectroscopic data and crucially these complexes possess a four-legged pianostool geometry at rhodium and long M---H distances (> 2.0 Å) that are conserved across a series (M = B, Si, Al, Zn, Mg). More recently Whittlesey, Macgregor and co-workers isolated a heterobimetallic complex in which Ru and Zn sites are bridged by two hydride ligands in a k 2 -fashion.…”

“…Two molecules are found within the asymmetric unit of Mg•Ru-N2, both are disordered with a second overlapping orientation and data are provided for the least disordered fragment.Bonding Analysis of M•Ru-N2:The metal---metal distances in M•Ru-N2 are all within the sum of the single bond radii as defined by Pauling21 and only the Ru---Zn distance is longer than the sum of the covalent radii defined by Pyykkö 22. We, and others, have considered normalised metal---metal bond distances and the formal shortness ratio as a crude metric to interrogate the nature of metal---metal bonds 11,[23][24][25]. The fsr of M•Ru-N2 determined using the Pauling radii are all ~1 and could be an indicator of a metal-metal bond (Al, 0.99; Zn, 1.00; Mg, 0.99).…”

A monomeric, heterobimetallic complex with an unsupported Mg–Fe bond

“…4 For unsupported bonds between a transition metal and an element from elsewhere in the periodic table, much recent progress has been made in the p-block, 5 lanthanides 6 and actinides, 4,7 which is facilitating the systematic study of the nature of the bonding between these elements. There is, however, a paucity of analogous complexes of the s-block elements, and it is only in the last few years that the number of compounds with direct, unsupported bonds between an alkaline earth (Ae) metal and a transition metal (TM) has started to gather pace in the literature, [8][9][10][11][12][13][14][15][16][17] and complexes featuring a Be−TM bond 11,16 and a Ca−TM bond 12 are incredibly scarce. The expansion of the scope of complexes featuring an unsupported bond between an alkaline earth and transition metal will aid the understanding of the fundamental structure and bonding within this family of heterobimetallic compounds.…”