The First Example of a Formal Scandium(I) Complex:  Synthesis and Molecular Structure of a 22-Electron Scandium Triple Decker Incorporating the Novel 1,3,5-Triphosphabenzene Ring

Gold(I) and Silver(I) Complexes of Diphosphacyclobutadiene Cobaltate Sandwich Anions

“…X-ray crystallography: The crystals were processed at Agilent Technologies SuperNova (3,7,8, and 9) and Bruker AXS APEX II (2 and 6) de-A C H T U N G T R E N N U N G vices, respectively. Either semi-empirical multi-scan absorption corrections [38] or analytical ones [39] were applied to the data.…”

“…[6] Since then, various heteroleptic diphosphacyclobutadiene complexes have been synthesized with a range of different early and late transition metals. [7] Homoleptic complexes, which exclusively contain two or three diphosphacyclobutadiene ligands (type B and C) are still rather scarce. [8,9] Only few metal complexes with diphosphacyclobutadiene metalloligands have been reported so far.…”

Phospha‐Organic Chemistry: Panorama and Perspectives

“…Among the most noteworthy structures are the slightly bent (angle between the planes 168), neutral, and diamagnetic hexaphosphatitanocene [Ti(h 5 -P 3 C 2 ) 2 ], [293] the paramagnetic pentaphosphavadanocene [V(h 5 -P 2 C 3 )(h 5 -P 3 C 2 )], [294] the hexaphosphachromocene [Cr(h 5 -P 3 C 2 ) 2 ], [295] the hexaphosphamanganocene [Mn(h 5 -P 3 C 2 ) 2 ] [296] which shows an unprecedented 2 A ground state, and the extraordinary 22-valence-electron triple decker [(h 5 -P 3 C 2 )Sc(m-33)Sc(h 5 -P 3 C 2 )]. [297] Other recent work includes the synthesis of Ga, In, and Tl derivatives [298,299] and several (h 5 -P 3 C 2 ) metal carbonyl complexes. [300] Several theoretical studies of such complexes are available, [296,299,301,302] one of which explains the diamagnetism of the hexaphosphatitanocene in terms of significant backdonation from the Ti center to the LUMO of the P 3 C 2 ring to form a d bond.…”

Metal-vapour synthesis of phospha-organometallic compounds: reaction of nickel atoms with the phospha-alkyne tBuCP. Structural characterisation of [Ni(η3-PC2tBu2)(η5-P3C2tBu2)], a derivative of the novel, aromatic phosphirenyl cation

“…Co-condensation of molybdenum or tungsten atoms with t BuCP on the other hand unexpectedly afforded red crystalline compounds of molecular formula [M( t BuCP) 6 ] (M = W, Mo), indicative of the assembly of six rather than five phospha-alkyne units around the metal centre affording an 18-electron diamagnetic compound. Contrary to expectations, the compounds formed were not the bis(g−triphosphabenzene) sandwich complexes [M(g 6 -P 3 C 3 t Bu 3 ) 3 ], but shown to be the homoleptic tris(1,3-diphosphacyclobutadiene) complexes [M(g 4 -P 2 C 2 t Bu 2 ) 3 ] (M=W, Mo) ( Fig.…”