Synthesis and structures of bis(iminophosphorano)methanide chelate complexes with zinc and group 13

Bi‐ and tridentate coordination behaviour of a novel bis(phosphinimino)methanide ligand

“…Thus, the methanide carbon atom acts here as Lewis base, which coordinates to the Lewis acidic AuC 6 F 5 . There are other heterobimetallic complexes based in the bis(phosphinimino)methane scaffold reported, e.g., [Ir(cod){(C 6 H 4 )(Ph)P(=NSiMe 3 )CHP(Ph) 2 =NSiMe 3 }Li(THF)] and AlCl 2 [C(Ph 2 P=NSiMe 3 ) 2 AlCl 3 ] [4a,5a] . However, both compounds are derivatives of the double‐deprotonated bis(phosphinimino)methandiide ligand.…”

Role of Bis(phosphinimino)methanides as Universal Ligands in the Coordination Sphere of Metals across the Periodic Table

“…34 All these metal complexes adopted distorted tetrahedral structures obtained by the tethering of monoanionic bis(phosphinimino)methanide ligands. 78 Complex 34 is a bimetallic carbene compound in which a heteroatomic sixmembered ring is formed by chelation of the bis-(phosphinimino)methandiide. In contrast, the reaction of 6a with the corresponding metal halide (MCl 3 or MBr 3 ) in a 1:1 molar ratio in THF afforded the singly protonated carboncoordinated compounds [{CH(Ph 2 PNSiMe 3 ) 2 }MCl 2 ] (M = Al (35), Ga (36), In (37)) and [{CH(Ph 2 PNSiMe 3 ) 2 }MBr 2 ] (M = Al (38), Ga (39), In (40)).…”

“…52 Cavell et al reported on the preparation of an aluminum complex of the composition [Li(THF) 4 ][{C(Ph 2 PNSiMe 3 ) 2 }-Al 2 Cl 5 ] (34) by the transmetalation reaction of the lithium methandiide complex [C(Ph 2 PNSiMe 3 ) 2 Li 2 ] 2 (6a) with AlCl 3 in a 1:4 molar ratio in THF (Scheme 8). 78 Complex 34 is a bimetallic carbene compound in which a heteroatomic sixmembered ring is formed by chelation of the bis-(phosphinimino)methandiide. In contrast, the reaction of 6a with the corresponding metal halide (MCl 3 or MBr 3 ) in a 1:1 molar ratio in THF afforded the singly protonated carboncoordinated compounds [{CH(Ph 2 PNSiMe 3 ) 2 }MCl 2 ] (M = Al (35), Ga (36), In (37)) and [{CH(Ph 2 PNSiMe 3 ) 2 }MBr 2 ] (M = Al (38), Ga (39), In (40)).…”

Phosphonium Ylides vs Iminophosphoranes: The Role of the Coordinating Ylidic Atom in cis-[Phosphine-Ylide Rh(CO)2] Complexes

“…In the case of phosphonium ylides, the ylidic bond was alternatively described in terms of donor–acceptor interactions between closed-shell R 3 P: and :CR 2 fragments with the contribution of two pairs of electrons . Beyond the difference in the electronegativity of the ylidic-type atom (C: 2.5 vs N: 3.0), phosphonium ylides and iminophosphoranes behave mainly as η 1 -ligands with strong σ-donor and relatively weak π-acceptor character either in main group or coordination chemistry . Moreover and especially compared to NHCs, while ylide-based ligands act as harder donors which, a priori, should be more prone to coordinate electropositive metals, their overall neutral character allows accommodating late metal elements, similarly to NHCs. , For catalytic purposes, examples involving P + –C – ylide ligands remain scarce, certainly due to synthetic and stability issues of the corresponding metal complexes .…”