Complexes of Iridium and Platinum Containing 5-Coordinated Phosphorus

Formation of a Trifluorophosphane Platinum(II) Complex by P−F Bond Activation of Phosphorus Pentafluoride with a Pt0Complex

“…Intramolecular rearrangement of 4 a to give trans ‐[(Me 3 P) 2 PtF(PF 4 )] and of [(Me 3 P) 2 Pt(PF 4 )] + to give 3 a are too high in energy to take place at low temperatures (see the Supporting Information). Furthermore, there is a precedent for the abstraction of a fluoride anion from a [PF 4 ] − complex in the literature: The reaction of [(Et 3 P) 2 Ir(CO)Cl 2 (PF 4 )] with BF 3 to give [(Et 3 P) 2 Ir(CO)Cl 2 (PF 3 )][BF 4 ] . Mechanisms related to that suggested for the transformation of 4 a into 3 a in Scheme have been predicted for the reaction of [(Me 3 P) 2 Pt→BF 3 ] with BF 3 to give trans ‐[(Me 3 P) 2 Pt(BF 2 )(FBF 3 )], and the reaction of [(Me 3 P) 2 Pt→SiF 4 ] with SiF 4 to give trans ‐[(Me 3 P) 2 Pt(SiF 3 )(FSiF 4 )], on the basis of DFT calculations .…”

“…[2] Thus, the synthesis of cis-[PtCl 2 (PF 3 ) 2 ]a nd [PtCl 2 (PF 3 )] 2 by Chatt and Williams in the early 1950 sm arks the start of the systematic development of the coordination chemistry of PF 3 . [3] Most PF 3 complexes wereo btained by the reaction of PF 3 with am etal precursor or by transformationo facomplex that already contains aP F 3 ligand.T he synthesis of PF 3 complexes by reaction of trans-[(Et 3 P) 2 Ir(CO)Cl]w ith PF 4 Ho rP F 4 Cl is an interesting route,b ut is somewhat limited in scope. [4] In addition to the large numbero fP F 3 transition-metal compounds,afew MÀPF 4 complexes are known: [5] for example, [(Et 3 P) 2 Ir(CO)Cl 2 (PF 4 )] [4,6] and [CpFe(CO) 2 (PF 4 )].…”

“…[3] Most PF 3 complexes wereo btained by the reaction of PF 3 with am etal precursor or by transformationo facomplex that already contains aP F 3 ligand.T he synthesis of PF 3 complexes by reaction of trans-[(Et 3 P) 2 Ir(CO)Cl]w ith PF 4 Ho rP F 4 Cl is an interesting route,b ut is somewhat limited in scope. [4] In addition to the large numbero fP F 3 transition-metal compounds,afew MÀPF 4 complexes are known: [5] for example, [(Et 3 P) 2 Ir(CO)Cl 2 (PF 4 )] [4,6] and [CpFe(CO) 2 (PF 4 )]. [7] Metallotetrafluorophosphoranes [L n M-PF 4 ] [5] can be regarded as complexes of the tetrafluorophosphite anion [PF 4 ] À .…”

Metallophosphoranes: The hidden face of transition metal–phosphine complexes

“…The first crystallographically characterized metallophosphorane, 1, was reported by Riess and coworkers in 1981 [4] and a search of the Cambridge Structural Database now reveals more than 30 metallophosphoranes, including examples from Group 6 (Mo [5]), Group 7 (Mn [6]), Group 8 (Fe [7], Ru [8]), Group 9 (Co [9], Rh [10], Ir [11]) and Group 10 (Ni [12], Pd [13], Pt [10b,14]). The structures of metallophosphoranes generally fall into two cat- egories -a simple 1 -binding mode through phosphorus (as in 2 [6], 3 [10a] and 4 [11]) and a 2 -binding mode, where a heteroatom substituent on phosphorus can also donate to the metal centre (as in 1).…”

“…The structures of metallophosphoranes generally fall into two cat- egories -a simple 1 -binding mode through phosphorus (as in 2 [6], 3 [10a] and 4 [11]) and a 2 -binding mode, where a heteroatom substituent on phosphorus can also donate to the metal centre (as in 1). In the former case the geometry around phosphorus is usually close to trigonal bipyramidal, whereas the 2 -species display more distorted structures and are formed when the metal centre would otherwise be unsaturated.…”