Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P-C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving initial oxidation of white phosphorus (P 4 ) with hazardous chlorine gas and the subsequent displacement of chloride ions. Catalytic P 4 organofunctionalisation reactions have remained elusive, as they require multiple P-P bond breaking and P-C bond formation events to break down the P 4 core, all of which must occur in a controlled manner. Herein, we describe an efficient transition metalcatalyzed process capable of forming P-C bonds from P 4 . Using blue light photocatalysis, this method directly affords valuable triarylphosphines and tetraarylphosphonium salts in a single reaction step.The academic, industrial and societal importance of phosphorus chemistry is difficult to overstate. Phosphorus is one of the six essential 'biogenic elements' required in large quantities by every living organism, and synthetic phosphorus compounds find myriad industrial and commercial applications due to their diverse array of useful chemical, physical and biological properties. 1 This importance is reflected in the fact that white phosphorus (P 4 ) is currently produced on an estimated scale of >1 Mt / year. 2 P 4 is by far the most reactive and industrially-relevant form of elemental phosphorus, and acts as the common precursor from which effectively all synthetic phosphorus-containing species are ultimately Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:
[Ar′SnCo]2 (1, Ar′ = C6H3-2,6{C6H3-2,6-iPr2}2), a rare metal–metal bonded cobalt–tin cluster with low-coordinate tin atoms, was prepared by the reaction of [K(thf)0.2][Co(1,5-cod)2] (cod = 1,5-cyclooctadiene) with [Ar′Sn(μ-Cl)]2. This reaction illustrates a promising synthetic strategy to access uncommon metal clusters. The structure of 1 features a rhomboidal Co2Sn2 core with strong metal–metal bonds between tin and cobalt and a weaker tin–tin interaction. Reaction of 1 with white phosphorus afforded [Ar′2Sn2Co2P4] (2), the first molecular cluster compound containing phosphorus, cobalt and tin.
The first homoleptic cobalt phosphanido complex [K(thf) ][Co{1,2-(PtBu ) C B H } ] (1) was prepared by an unprecedented oxidative P-P bond addition of an ortho-carborane-substituted 1,2-diphosphetane to cobalt(-I) in [K(thf) ][Co(η -cod) )] (cod=1,5-cycloctadiene). Compound 1 is a rare distorted tetrahedral 3d complex with a low-spin ground state configuration. Magnetic measurements revealed that the complex is diamagnetic between 2 to 270 K in the solid state and at 298 K in [D ]THF solution. Based on DFT calculations, the unusual singlet ground state is caused by the strong σ-donor and moderate π-donor properties of the bis(phosphanido) ligand.
The homoleptic 1,3-diphosphacyclobutadiene sandwich complex [Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 ] À behaved as av ersatile and highly flexible metalloligand toward Ni 2 + ,R u 2 + , Rh + ,a nd Pd 2 + cations, formingarange of unusual oligonuclear compounds. The reactiono f[ K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with [Ni 2 Cp 3 ]BF 4 initially afforded the s-complex [CpNi{Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }(thf)] (2), which converted into [Co(h 4 -CpNi{1,3-P 2 C 2 tBu 2 -kP,kC})(h 4 -1,3-P 2 C 2 tBu 2 )] (3)b elow room temperature. The structure of 3 contains an unprecedented 1,4-diphospha-2-nickelacyclopentadiene moiety formed by an oxidative addition of al igand PÀCb ond onto nickel. At elevated temperatures, 3 isomerized to [Co(h 4 -CpNi{1,4-P 2 C 2 tBu 2 -k 2 P, P })(h 4 -1,3-P 2 C 2 tBu 2 )] (4), which features a1 ,3-diphospha-2-nickelacyclopentadiene unit. Transmetalation of [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with [Cp*RuCl] 4 (Cp* = C 5 Me 5 )a fforded tetranuclear[ (Cp*Ru) 3 (m-Cl) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] (5), in which the [Co(h 4 -1,3-P 2 C 2 tBu 2 ] À aniona cts as ac helate ligand toward Ru 2 + .T he diphosphido complex [(Cp*Ru) 2 (m,h 2 -P 2 )(m,h 2 -C 2 tBu 2 )] (6)w as formed as ab yproduct. Pure compound 6 was isolated after prolonged heating of the reaction mixture. The reaction of [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 R 2 ) 2 }] (R = tBu;a damantyl, Ad) with [RhCl(cod)] 2 (cod = 1,5-cyclooctadiene) afforded unprecedented p-complexes [Rh(cod){Co(h 4 -1,3-P 2 C 2 R 2 ) 2 }] (7:R = tBu; 8:R= Ad), in which one m:h 4 :h 4 -P 2 C 2 R 2 ligand bridges two metal atoms.T he pentanuclear complex [Pd 3 (PPh 3 ) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 } 2 ]( 10), featuring aP d 3 chain andarare 1,4-diphospha-2-butene ligand,w as synthesized by reacting [K(thf) 2 {Co(h 4 -1,3-P 2 C 2 tBu 2 ) 2 }] with cis-PdCl 2 (PPh 3 ) 2 .T he redox properties of selected compounds were analyzed by cyclic voltammetry, whereas DFT calculations gave additional insighti ntot he electronic structures.The results of this study revealed several remarkable and previously unrecognized properties of the [Co(P 2 C 2 tBu 2 ) 2 ] À anion.Scheme1.Synthesis of complexes of type A. [7] [a] C. Rçdl,P rof. Dr.R.W olf
Complexes [(C 4 Me 4 )Co(CO) 2 {Co(P 2 C 2 tBu 2 ) 2 }](1, C 4 Me 4 = tetramethylcyclobutadiene) and [CpNi{Co(P 2 C 2 tBu 2 ) 2 }-(PPh 3 )] (2, Cp = cyclopentadienyl) were synthesized by transmetalating [Tl(thf ) 2 {Co(P 2 C 2 tBu 2 ) 2 }] with [(C 4 Me 4 )Co(CO) 2 I] and [CpNiBr(PPh 3 )]. Compounds 1 and 2 were fully characterized by X-ray crystallography, multinuclear NMR, UV/Vis, and IR spectroscopy, and elemental analysis. Their molecular structures show σ-coordination of one phosphorus atom of the [Co(P 2 C 2 tBu 2 ) 2 ]anion to the second metal atom (cobalt or nickel). Time-dependent density functional theory (TD-DFT) calculations were [a]
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