A DFT Study on Dinuclear Metallocenes RMMR [R= (BCO)₅, (BNN)₅; M = Be, Mg, Ca, Zn, Cd]

Abstract

A series of dinuclear metallocenes with formula RMMR [R= (BCO)5, (BNN)5; M = Be, Mg, Ca, Zn, Cd] are investigated via density functional theory. All these compounds contain two M[eta5-(BCO)5] fragments or two M[eta5-(BNN)5] fragments with a direct metal-metal single sigma bond. Detailed NBO analyses show that the metal-ligand interactions are predominantly ionic in nature and each metal atom is in its +1 oxidation state. NBO analyses indicate that the interaction between the B-B bonds and metal-metal antibond has played a role in the stabilities of these compounds.

Ultrashort Mn–Mn Bonds in Organometallic Complexes

“…Similarly, many different central metal atoms have been studied, leading to alkaline-earth dimetallocenes [39][40][41][42], transition metal dimetallocenes [43][44][45], heterodinuclear compounds [46,47] and zinc isoelectronic elements, such as Cd and Hg [48]. Although multinuclear metallocenes of Co, Cu, and Ni, and other transition metals have been described [43][44][45][49][50][51][52][53][54], the study of larger manganese benzene compounds is still to be done.…”

“…Different external molecules have been considered, such as Bz, cyclopentadiene, and even fullerenes . Similarly, many different central metal atoms have been studied, leading to alkaline-earth dimetallocenes, − transition metal dimetallocenes, − heterodinuclear compounds, , and zinc isoelectronic elements, such as Cd and Hg . Although multinuclear metallocenes of Co, Cu, Ni, and other transition metals have been described, − ,− the study of larger manganese benzene compounds is still to be done.…”

Binuclear Alkaline Earth Metal Compounds (Be, Mg, Ca, Sr, Ba) with α-Diimine Ligands: A Computational Study

“…A series of dimeric compounds RMMR [R = (BCO) 5 , (BNN) 5 ; M = Be, Mg, Ca, Zn, Cd] were investigated by Li and co-workers. 15 Although experimental approaches to stable binuclear metallocenes have not so far been successful for Ae elements, in 2007 Green, Jones, and Stasch 16 reported in Science two molecular MgÀMg-bonded compounds with the magnesium metal in the þ1 oxidation state, RMgMgR (R 1 = [(Ar)NC(N i Pr 2 )N(Ar)] À ; R 2 = {[(Ar)NC(Me)] 2 CH} À , where Ar is 2,6-diisopropylphenyl). This achievement confirmed the theoretical prediction of MgÀ Mg bond formation.…”

Mg2H2: New insight on the Mg–Mg bonding and spectroscopic study

“…[1][2][3] and RMg-MgX (X = F, Cl) during the formation of Grignard reagents. Recently, focus was made on alkaline earth (group 2) and group 12 atoms.…”