The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P5R2]+ cations with cyclopentadienyl metal complexes. The reaction of [CpArFe(μ‐Br)]2 (CpAr=C5(C6H4‐4‐Et)5) with [P5R2][GaCl4] (R=iPr and 2,4,6‐Me3C6H2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1‐R, R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[CpAr] and [P5R2][GaCl4]. The cationic complexes [CpArCo(η4‐P5R2)][GaCl4] (2‐R[GaCl4], R=iPr and Cy) and [(CpArNi)2(η3:3‐P5R2)][GaCl4] (3‐R[GaCl4]) were obtained from [P5R2][GaCl4] and [CpArM(μ‐Br)]2 (M=Co and Ni) as well as by using low‐valent “CpArMI” sources. Anion metathesis of 2‐R[GaCl4] and 3‐R[GaCl4] was achieved with Na[BArF24]. The P5 framework of the resulting salts 2‐R[BArF24] can be further functionalized with nucleophiles. Thus reactions with [Et4N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl.
The divalent iron complexes trans-[FeBr 2 (BINC) 2 ], [Cp*FeCl(BINC)] (Cp* = Me 5 C 5 ), and [FeBr 2 (CNAr 3 NC) 2 ] with the chelating bis(isonitrile) ligands BINC (bis(2-isocyanophenyl)phenylphosphonate) and CNAr 3 NC (2,2″-diisocyano-3,5,3″,5"tetramethyl-1,1′:3′,1″-terphenyl) have been prepared and characterized. Their subsequent reduction yields the di-and trinuclear compounds [Fe 3 (BINC) 6 ], [Cp*Fe(BINC)] 2 , [Fe(CNAr 3 NC) 2 ] 2 , and [K-(Et 2 O)] 2 [Fe(CNAr 3 NC) 2 ] 2 . The molecular structures of all new species were determined by X-ray crystallography and compared to those of related iron carbonyl complexes, demonstrating that the bidentate isonitrile ligands are capable surrogates for two CO ligands with only minimal distortion of the tetrahedral or octahedral geometry of the parent complexes. The complexes were further characterized by NMR and IR spectroscopy, and the electrochemical properties of selected compounds were analyzed by UV−vis−NIR spectroelectrochemistry.
The coordination chemistry of phosphinines (phosphabenzenes) has been intensively investigated over the last decades, but metal complexes of halophosphinines and related halide-substituted phosphacyclohexadienyls have remained scarce.
The synthesis and characterization of two heterobimetallic complexes [K([18]crown‐6){(η4‐C14H10)Fe(μ‐η4:η2‐P4)Ga(nacnac)}] (1) (C14H10 = anthracene) and [K(dme)2{(η4‐C14H10)Co(μ‐η4:η2‐P4)Ga(nacnac)}] (2) with strongly reduced P4 units is reported. Compounds 1 and 2 are prepared by reaction of the gallium(III) complex [(nacnac)Ga(η2‐P4)] (nacnac = CH[CMeN(2,6‐iPr2C6H3)]2) with bis(anthracene)ferrate(1–) and ‐cobaltate(1–) salts. The molecular structures of 1 and 2 were determined by X‐ray crystallography and feature a P4 chain which binds to the transition metal atom via all four P atoms and to the gallium atom via the terminal P atoms. Multinuclear NMR studies on 2 suggest that the molecular structure is preserved in solution.
A ternary Ni2Si2P8 cluster compound is formed selectively by thermolysis of a well-defined nickel complex. This reaction illustrates a potentially useful strategy for the preparation of heteroatom-doped transition metal-phosphide clusters.
The neutral, homoleptic pyridylphosphininenickel(0) complex 6-Ph 2 -PC 5 H 2 ) 2 ] (1) has been obtained by reaction of the formal Ni(0) source [(IPr)Ni(H 2 CCHSiMe 3 ) 2 ] with 2 equiv of 2-(2′-pyridyl)-4,6-diphenylphosphinine (L). Compound 1 can be oxidized both electrochemically and through the use of ferrocenium salts, to afford the corresponding Ni(I) complexes [1]BF 4 , [1(THF)]PF 6 , and [1 2 ](BAr F 4 ) 2 . The structures of these salts reveal an interesting dependence on the nature of the anion. While [1]BF 4 and [1(THF)]PF 6 show trigonal-bipyramidal coordination of Ni in the solid state, [1 2 ](BAr F 4 ) 2 exists as a dinuclear Ni(I) complex and possesses a bridging phosphinine moiety in a rare μ 2 mode. Reactions of 1 with halobenzenes highlight the noninnocent behavior of the aromatic phosphinine ligand, leading to the formation of oxidized Ni complexes but not to classical oxidative addition products. The reaction of 1 with bromobenzene affords the λ 5 phosphinine 2 and the bipyramidal Ni(I) complex [1]Br, whereas a more unconventional oxidation product 3 is formed from the reaction of 1 and iodobenzene.
The chemistry of polyphosphorus cations has rapidly developed in recent years,b ut their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P 5 R 2 ] + cations with cyclopentadienyl metal complexes.T he reaction of [Cp Ar Fe(m-Br)] 2 (Cp Ar = C 5 (C 6 H 4 -4-Et) 5 )with [P 5 R 2 ][GaCl 4 ](R= iPr and 2,4,6-Me 3 C 6 H 2 (Mes)) afforded bicyclo[1.1.0]pentaphosphanes (1-R,R = iPr and Mes), showing an unsymmetric "butterfly" structure.The same products 1-R were formed from K[Cp Ar ]a nd [P 5 R 2 ][GaCl 4 ]. The cationic complexes [Cp Ar Co(h 4 -P 5 R 2 )][GaCl 4 ]( 2-R-[GaCl 4 ], R= iPr and Cy) and [(Cp Ar Ni) 2 (h 3:3 -P 5 R 2 )][GaCl 4 ] (3-R[GaCl 4 ]) were obtained from [P 5 R 2 ][GaCl 4 ]and [Cp Ar M-(m-Br)] 2 (M = Co and Ni)a sw ell as by using low-valent "Cp Ar M I "s ources.A nion metathesis of 2-R[GaCl 4 ]a nd 3-R[GaCl 4 ]w as achieved with Na[BArF 24 ]. The P 5 framework of the resulting salts 2-R[BArF 24 ]c an be further functionalizedwith nucleophiles.Thus reactions with [Et 4 N]X (X = CN and Cl) give unprecedented cyano-and chlorofunctionalizedcomplexes,while organo-functionalizationw as achieved with CyMgCl.
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