Use of 1,3‐diphosphacyclobutadiene complexes in the synthesis of mixed metal aggregates containing cobalt, rhodium, and platinum: Structure of a hexarhodium complex

Hitchcock, Peter B.; Maah, Mohd Jamil; Nixon, John F.

doi:10.1002/hc.520020207

Cited by 20 publications

(2 citation statements)

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“…The first examples of bi‐ and trimetallic diphosphacyclobutadiene compounds were complexes D and E , which were obtained from [CpCo(P 2 C 2 t Bu 2 ) 2 ] (type A , Figure 1) and one or two equivalents of [CpCo(C 2 H 4 ) 2 ] 2a–2d. Complexes of the neutral type A species with rhodium(I), platinum(II) and platinum(0), tungsten(0), and copper(I) have also been described 2e,2n. Stone and co‐workers reported heterobimetallic rhodium–cobalt and rhodium–gold complexes F and G , which contain an anionic 1,3‐diphosphacyclobutadiene metalla‐1,2‐dicarbaborate ligand 9.…”

Section: Introductionmentioning

confidence: 99%

Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions

Rödl

Wolf

2015

Eur J Inorg Chem

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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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Section: Introductionmentioning

confidence: 99%

Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions

Rödl

Wolf

2015

Eur J Inorg Chem

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“…[6c, [10][11][12][13] Examples are the oligonuclear compounds D-F, which were obtained by treating type A complexes [CpM(h 4 -P 2 C 2 R 2 ) 2 ] (R= tBu, iPr) with [CpCoA C H T U N G T R E N N U N G (h [6c, 10] The (1,2-dicarbaborane)rhodium complex G is the only complex in which a 1,3-diphosphacyclobutadiene ligand is coordinated to a coinage metal atom, more specifically gold(I). (7), and [K( [18]crown-6)A C H T U N G T R E N N U N G (thf) 2 ][M{Co-A C H T U N G T R E N N U N G (P 2 C 2 Ad 2 ) 2 } 2 ] (8: M= Au 9: M= Ag) in moderate yields.…”

Section: Introductionmentioning

confidence: 99%

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

Malberg

Wiegand

Eckert

et al. 2013

Chemistry A European J

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The synthesis and structural characterization of the first coordination compounds of bis(diphosphacyclobutadiene) cobaltate anions [M(P(2)(2)R(2))(2)](-) is described. Reactions of the new potassium salts [K(thf)(3){Co(η(4)-P(2)C(2)tPent(2))(2)}] (1) and [K(thf)(4){Co(η(4)-P(2)C(2)Ad(2))(2)}] (2) with [AuCl(tht)] (tht = tetrahydrothiophene), [AuCl(PPh(3))] and Ag[SbF(6)] afforded the complexes [Au{Co(P(2)C(2)tPent(2))(2)}(PMe(3))(2)] (3), [Au{Co(P(2)C(2)Ad(2))(2)}](x) (4), [Ag{Co(P(2)C(2)Ad(2))(2)}](x) (5), [Au(PMe(3))(4)][Au{Co(P(2)C(2)Ad(2))(2)}(2)] (6), [K([18]crown-6)(thf)(2)][Au{Co(P(2)C(2)Ad(2))(2)}(2)] (7), and [K([18]crown-6)(thf)(2)][M{Co(P(2)C(2)Ad(2))(2)}(2)] (8: M = Au 9: M = Ag) in moderate yields. The molecular structures of 2 and 3, and 6-9 were elucidated by X-ray crystallography. Complexes 4-9 were thoroughly characterized by (31)P and (13)C solid state NMR spectroscopy. The complexes [Au{Co(P(2)C(2)Ad(2))(2)}](x) (4) and [Ag{Co(P(2)C(2)Ad(2))(2)}](x) (5) exist as coordination polymers in the solid state. The linking mode between the monomeric units in the polymers is deduced. The soluble complexes 1-3, 6, and 7 were studied by multinuclear (1)H-, (31)P{(1)H}-, and (13)C{(1)H} NMR spectroscopy in solution. Variable temperature NMR measurements of 3 and 6 in deuterated THF reveal the formation of equilibria between the ionic species [Au(PMe(3))(4)](+), [Au(PMe(3))(2)](+), [Co(P(2)C(2)R(2))(2)](-), and [Au{Co(P(2)C(2)R(2))(2)}(2)](-) (R = tPent and Ad).

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Homoleptic Phosphaalkyne Complexes of Silver(I)

et al. 2016

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By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}3], [Al{OC(CF3)3}4]), two phosphaalkynes could be coordinated side‐on to a bare silver(I) center to form the unprecedented homoleptic complexes [Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] (1) and [Ag(η2‐P≡CtBu)2][Al{OC(CF3)3}4] (2). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square‐planar coordination mode of the phosphaalkynes at Ag+ was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH3)2CO)Ag(η2‐P≡CtBu)2][FAl{OC12F15}3] (3) and [(C7H8)2Ag(η2‐P≡CtBu)][FAl{OC12F15}3] (4). All of the compounds were comprehensively characterized in solution and in the solid state.

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Use of 1,3‐diphosphacyclobutadiene complexes in the synthesis of mixed metal aggregates containing cobalt, rhodium, and platinum: Structure of a hexarhodium complex

Abstract: ABSTRACT

Cited by 20 publications

References 25 publications

Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions

Cobalt(I) and Nickel(II) Complexes of Bis(1,3‐diphosphacyclobutadiene) Sandwich Anions

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

Homoleptic Phosphaalkyne Complexes of Silver(I)

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