Di-ortho-beryllated Carbodiphosphorane: A Compound with a Metal–Carbon Double Bond to an Element of the s-Block

Abstract

Double bonds have been realized for a wide variety of elements in the p-, d-, and f-blocks. However, no s-block metal complexes with a double bond have been identified. Here we report the synthesis and characterization of a di-ortho-beryllated carbodiphosphorane, which exhibits a double dative BeC bond. This species shows an unprecedented bonding situation at the metal center, which was extensively analyzed by experimental and computational means.

s‐Block Multiple Bonds: Isolation of a Beryllium Imido Complex

“…The bonding situation and electronic properties in D were investigated by DFT calculations, indicating that the Be−N bond is strongly polarized which can be described as predominantly ionic with partial Be−N double bond character [Be1−N1 1.525(2), Be1−N2 1.519(2)]. Very recently, Buchner, Frenking, and Sundermeyer reported a beryllated carbodiphosphorane which features an s‐block metal‐carbon double bond, the first of its kind (Figure 1, E ) [18] …”

“…The WBI value for both Be−N bonds in 2 are greater than that of the Be−C bond in E (WBI=0.12). Buchner, Frenking, and Sundermeyer have highlighted the failure of the NBO method to provide a chemically intuitive description for Be as it only considers the 2s AO and omits the important 2p AO [18, 28] . The NBO charge on the Be atom is rather large (+1.64 e).…”

Bonding in M(NHBMe)2 and M[Mn(CO)5]2 complexes (M=Zn, Cd, Hg; NHBMe=(HCNMe)2B): divalent group 12 metals with zero oxidation state

“…One of the strengths of this method is that if there are more than one partitioning scheme available, one can choose the most suitable scheme to describe the bonding by using the size of ΔE orb as a probe. For a given interaction, those fragments, which give the lowest ΔE orb value, are the best one to describe the bonding situation as it indicates that the chosen fragments are most nearly prepared as those in the complex [69][70][71][72][73][74]. For both M(NHB Me ) 2 and M[Mn(CO) 5 ] 2 complexes, we have carried out EDA by considering M and (L) 2 with different charges and electronic states as interacting fragments.…”

Bonding and Stability of C6F4 Bridged by Bis‐Carbenes: EDA‐NOCV Analysis of (L)2C6F4 [L = SNHCDip, cAACMe]

“…in 2006 showed the formation two Ph 3 P→C dative σ‐bonds and Ph 3 P←C π‐bonds leading to the accumulations of two lone pairs of electrons on the central excited singlet C‐atom [7] . These lone pairs of electrons on C‐atom of C(PPh 3 ) 2 are donatable to the acceptors making a C‐atom double σ‐donor which is a remarkable feature of such a stable complex [8a–b] . The notation of arrow for a dative bond was originally introduced by Sidgwick in the 1920 s [8c] and it was implemented for divalent carbon(0) compounds L→C←L as suggested by Varshavskii in 1980 [8d–e] .…”