PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

Scherer, Otto J.; Weigel, Sascha; Wolmershäuser, Gotthelf

doi:10.1002/(sici)1098-1071(1999)10:7<622::aid-hc16>3.0.co;2-u

Cited by 13 publications

(2 citation statements)

References 24 publications

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“…M ) Ag, Y ) ClO 4 , PF 6 (164)]. 133 The analogous rhodium/ silver trinuclear complex, [{(triphos)Rh(µ,η 3:2 -cyclo-P 3 )} 2 Ag]Y, [Y ) OTf, PF 6 (165)] was also prepared from 144 and the appropriate silver salt AgY. Trinuclear gold complexes of formula [{(triphos)M(µ,η 3:2 -cyclo-P 3 )} 2 Au]PF 6 [M ) Co ( 166), Rh (167), Ir (168)] were also prepared for the three isomorphous [{(triphos)M(η 3 -cyclo-P 3 )}] complexes by reaction with gold(I) chloro derivatives in the presence of thallium hexafluorophosphate as chloride scavenger (see section 5.3).…”

Section: Cobaltmentioning

confidence: 99%

P₄ Activation by Late-Transition Metal Complexes

et al. 2010

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Introduction 4178 2. Group 7 Metals 4180 2.1. Manganese 4180 2.2. Rhenium 4180 3. Group 8 Metals 4182 3.1. Iron 4182 3.1.1. Iron Complexes Containing P 4 and P n Ligands Resulting from the Degradation of the P 4 Tetrahedron (n < 4) 4182 3.1.2. Synthesis, Coordination Chemistry, and Reactivity of Pentaphosphaferrocene 4187 3.1.3. Polymers and Supramolecular Assemblies Based on the Pentaphosphaferrocene Building Block 4194 3.1.4. Polyphosphorus Ligands, P x (x > 5) 4197 3.2. Ruthenium 4197 3.3. Osmium 4201 4. Group 9 Metals 4202 4.1. Cobalt 4202 4.2. Rhodium 4215 4.3. Iridium 4220 5. Group 10 Metals 4222 5.1. Nickel 4222 5.2. Palladium 4227 5.3. Platinum 4227 6. Group 11 Metals 4229 6.1. Copper 4229 6.2. Silver 4230 6.3. Gold 4231 7. Abbreviations 4232 8. Acknowledgments 4232 9. References 4232 † This contribution is dedicated to our colleague and friend Prof. Piero Stoppioni on occasion of his 65th birthday and in recognition of his outstanding achievements in the field of white phosphorus activation. ‡ Note: In figures showing X-ray crystal structures, H atoms are generally omitted for clarity unless specified.

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Section: Cobaltmentioning

confidence: 99%

P₄ Activation by Late-Transition Metal Complexes

et al. 2010

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“…5 Similarly, oxidation of a µ 3phosphide complex was used to form the phosphorus monoxide clusters [(Cp′) 3 Co 3 (µ 3 -CC(CH 3 ) 3 )(µ 3 -PO)] (Cp′ ) η 5 -C 5 H 4 CH 2 CH 2 P(S)Bu t 2 ) 6 and [η 5 -C 5 H 5 (CO) 2 Mo] 3 PO as well as W and mixed MoW analogues of the latter. 7 The complex [{Cp′′Co} 3 (µ 3 -PO) 2 ] (Cp′′ ) η 5 -C 5 H 3 Bu t 2 -1,3), which contains two PO ligands, was formed by oxidation of the appropriate bis-phosphide complex, 8 while [{η 5 -(CH 3 ) 5 C 5 Fe}{Cp′′Co} 2 (µ 3 -PO)(µ 4 -P 2 O)(µ 2 -P 2 )] results from oxidation of [{η 5 -(CH 3 ) 5 C 5 Fe}{Cp′′Co} 2 (P 4 )-(P)]. 9 The only example of a mononuclear PO complex, (OP)Mo[N(R)Ar] 3 (R ) C(CD 3 ) 2 Me, Ar ) 3,5-C 6 H 3 Me 2 ), was formed by oxidation of the corresponding terminal phosphide complex.…”

Section: Introductionmentioning

confidence: 99%

Electronic Structures of Transition Metal Phosphorus Monoxide Complexes

et al. 2000

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Density functional theory calculations were carried out on the transition metal phosphorus monoxide complexes (CO) 12 PO] -, and [Ru 5 (CO) 15 PO] -. The results indicate that π-bonding dominates the interaction of PO with transition metal clusters and that electrostatic effects, as well as orbital interactions, have a significant influence on the PO bond strength and can lead to IR frequencies above that of free PO.

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Terminally Coordinated AsS and PS Ligands

Baláȥs

Green

Scheer

2006

Chemistry A European J

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The terminal AsS and PS complexes [(N(3)N)W(ES)] (N(3)N=N(CH(2)CH(2)NSiMe(3))(3); E=P (3), As (4)) were synthesised by reaction of [(N(3)N)W[triple chemical bond]As] and [(N(3)N)W[triple chemical bond]P], respectively, with cyclohexene sulfide. Both complexes present very short W--E and E--S bond lengths. The bonding was investigated by density functional theory (DFT) calculations using the fragment calculation method and natural bond orbital (NBO) analysis. According to the fragment analysis, in which the complexes were separated in an ES and a (N(3)N)W fragment, the bonding in complexes 3, 4 and [(N(3)N)W(SbS)] (5) is realised over a set of two sigma (1 sigma and 2 sigma) and two degenerate pi molecular orbitals (MOs) (1 pi and 2 pi). The 1 sigma MO is a bonding MO extended over the N(ax)-W-E-S core, whereas the 2 sigma MO is localised mainly on the E-S fragment. The 1 pi set is a E-S localised bonding molecular orbital, whereas the 2 pi set is in phase with respect to W-E but in antiphase with respect to E-S. Both methods indicate bond orders around two for both the E--S and the W--E bonds. The polarity of the complexes was examined by Hirshfeld charge analysis. This shows that complexes 3 and 4 are only slightly polarised, whereas 5 is moderately polarised toward the sulphur. As suggested by the computational results, the pi system in complexes 3-5 is best described by two three-centre four-electron bonds.

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PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

Cited by 13 publications

References 24 publications

P₄ Activation by Late-Transition Metal Complexes

P₄ Activation by Late-Transition Metal Complexes

Electronic Structures of Transition Metal Phosphorus Monoxide Complexes

Terminally Coordinated AsS and PS Ligands

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PX (X = O, S, Se, Te) and P4Se as ligands in multinuclear CpR-cobalt complexes

Cited by 13 publications

References 24 publications

P4 Activation by Late-Transition Metal Complexes

P4 Activation by Late-Transition Metal Complexes

Electronic Structures of Transition Metal Phosphorus Monoxide Complexes

Terminally Coordinated AsS and PS Ligands

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P₄ Activation by Late-Transition Metal Complexes

P₄ Activation by Late-Transition Metal Complexes