Synthesis and Structural Characterization of an Unusual Platinum π-Arene Complex: (η6-C6H3Me3)Pt[(C2F5)2PMe]Me+

Thapaliya, Bhusan; Debnath, Suman; Arulsamy, Navamoney; Roddick, Dean M.

doi:10.1021/acs.organomet.5b00410

Cited by 4 publications

(1 citation statement)

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“…Arene complexes of the heavier group 10 metals are much rarer. While a handful of cationic palladium(II) and platinum(II) arene half-sandwich complexes, such as II and III , have been structurally characterized − and shown some promise in catalytic applications, ,, examples of zerovalent heavier group 10 arene complexes remain very limited. The only crystallographically authenticated palladium(0) arene half-sandwich complexes are a couple of terphenylstannylene palladium complexes, in which the arene···Pd interaction is enforced through tethering with a terphenylstannylene unit, and the Pd center is stabilized by an additional phosphine ( IV ) or stannylene donor. , To date, there are no known examples of platinum(0) arene complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes

Dietz,

Arrowsmith,

Endres

et al. 2023

J. Am. Chem. Soc.

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A cyclic alkyl(amino)carbene (CAAC)-stabilized 1,4-diborabenzene (DBB, 1) reacts with the group 10 precursor [Ni(CO) 4 ] to yield the DBB pogo-stick complex [(η 6 -DBB)Ni-(CO)] (2) as a dark-green crystalline solid. The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong π-donor properties of the DBB ligand. The reaction of 1 with [M(nbe) 2 ] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(η 6 -DBB)M(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S 0 →S 1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (d xz or d yz ) to a d orbital located in the xy plane (d xy or d x 2 −y 2 ), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2π* orbital destabilizes the DBB•••Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe(CO) 5 ] to yield the doubly CO-bridged M(0)→ Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn−H addition with Ph 3 SnH to yield the corresponding Pt(II) stannyl hydride, [(η 6 -DBB)PtH(SnPh 3 )] (5).

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