Organometallic Molybdenum(V) Complexes with Primary Phosphine Ligands. Syntheses, Spectroscopic Properties and Molecular Structures of [Cp°MoCl4(PH2R)] (R = But, 1‐Ad, Cy, Ph, 2, 4, 6‐Me3C6H2, 2, 4, 6‐Pri3C6H2, Cp° = C5EtMe4)

Felsberg, Reinhard; Blaurock, Steffen; Junk, Peter Courtney; Kirmse, R.; Voigt, Andreas; Hey‐Hawkins, Evamarie

doi:10.1002/zaac.200300413

Cited by 16 publications

(9 citation statements)

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“…In addition, we obtained the complexes [Cp • MoCl 2 ( 3 -P 4 HCy 4 )] (11) and [Cp • 2 Mo 2 (-Cl) 2 (-P 4 Ph 4 )] (12) in very low yield by reaction of the paramagnetic molybdenum phosphane complexes [Cp • MoCl 4 (PH 2 R)] (Cp • = 5 -C 5 EtMe 4 , R = Cy or Ph) with two equivalents of NEt 3 ; the mechanism of this reaction was unclear, but could involve an intermediate molybdenum phosphinidene complex (Method 4) [22].…”

Section: General Synthetic Methods For the Preparation Of Metal Oligomentioning

confidence: 99%

“…Furthermore, reactions of the in situ generated analogous (P 4 HMes 4 ) − anion with rhodium(I) salts allowed for the first time the rational synthesis of a transition metal tetraphosphanido complex with a (P 4 HMes 4 ) − ligand, namely [Rh(P 4 HMes 4 )(cod)] (49) (Scheme 16) [47], while [Cp • MoCl 2 ( 3 -P 4 HCy 4 )] (11) was only obtained in very low yield via the reaction of [Cp • MoCl 4 (PH 2 Cy)] with two equivalents of NEt 3 [22]. The formation of 49 was always accompanied by [{Rh(cod)} 2 (-P 2 HMes 2 )(-PHMes)] (50); successive recrystallizations allowed both complexes to be separated.…”

Section: Reactivity Of the (P 4 R 4 ) 2− Ion Towards Transition Metalsmentioning

confidence: 99%

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The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Gómez‐Ruiz

Hey‐Hawkins

2011

Coordination Chemistry Reviews

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Section: General Synthetic Methods For the Preparation Of Metal Oligomentioning

confidence: 99%

Section: Reactivity Of the (P 4 R 4 ) 2− Ion Towards Transition Metalsmentioning

confidence: 99%

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Gómez‐Ruiz

Hey‐Hawkins

2011

Coordination Chemistry Reviews

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“…The structure of 8 was confirmed by an independent synthesis using unsymmetrical diphosphine 12 , which was prepared from PMe(Is)(Cl) and LiPHIs (Scheme ). As in related procedures, this gave a mixture of 12 (major product, about 60% of the mixture) and two symmetrical diphosphines, the known IsHP-PHIs ( 13 ) , and the new IsMeP-PMeIs ( 14 ), about 24 and 16%, respectively. This mixture was characterized by 1 H and 31 P NMR spectroscopy, and by mass spectrometry.…”

Section: Resultsmentioning

confidence: 69%

“…This diphosphine has been mentioned several times in the literature, but with limited experimental details. , Only 31 P{ 1 H} NMR data and the mass spectrum seem to have been reported . We describe a new synthesis and additional characterization data .…”

Section: Methodsmentioning

confidence: 93%

Rhodium-Catalyzed Isomerization of a Bis(secondary phosphine) to an Unsymmetrical Diphosphine via P–C Cleavage and P–P and C–H Bond Formation

2017

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To develop Rh-catalyzed dehydrocoupling for stereocontrolled synthesis of P−P bonds, we prepared potential intermediates, chiral rhodium phosphine-phosphido complexes, and investigated their stoichiometric and catalytic transformations. Treatment of [Rh(diphos*)(COD)][X] with the bis(secondary phosphine) IsHPCH 2 PHIs (1, Is = 2,4,6-(i-Pr) 3 C 6 H 2 ) gave the cations [Rh(diphos*)(IsHPCH 2 PHIs)][X] (diphos* = (R,R)-Me-DuPhos (2), (R,R)-i-Pr-DuPhos (3), or (R,R)-Me-BPE (4); X = BF 4 or OTf) with high diastereoselectivity as single C 2 -symmetric diastereomers. Deprotonation of 2−4 with NaN(SiMe 3 ) 2 yielded phosphine-phosphido chelates Rh(diphos*)(IsHPCH 2 PIs) 5−7 with high diastereoselectivity. Thermolysis of 5−7 in toluene at 90 °C caused isomerization to give Rh(diphos*)(IsMeP-PIs) (8−10) as mixtures of diastereomers. Under catalytic conditions, Rh-DuPhos precursors slowly converted 1 to a mixture of diastereomers of its isomer, the unsymmetrical diphosphine IsHP-PMeIs ( 12). We propose a possible mechanism for the isomerization and discuss its relationship to dehydrocoupling catalysis.

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“…304 [MoS 4 ] 2À mode assignments were also reported for substituted ammonium salts of this anion. 309 Resonance Raman data for [( t BuCO 2 ) 3 W 2 ] 2 (m-2,5-Th(CO 2 ) 2 include n s W 4 at 316 cm À1 and n s WO br at 472 cm À1 . 306 The complex {[Mo 3 S 7 Br 6 ] 2 } 4À , and related species, show nMo-m 2 -S in the range 400-580 cm À1 .…”

Section: Chromium Molybdenum and Tungstenmentioning

confidence: 99%

Vibrational spectra of transition element compounds

Davidson¹

Spectroscopic Properties of Inorganic and Organometallic Compounds

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Scandium, yttrium and the lanthanidesLaser-ablated scandium atoms react with H 2 O/N 2 mixtures to give matrix-trapped (Z 1 -N 2 )Sc(H)OH, (Z 1 -N 2 ) 2 Sc(H)OH and (Z 2 -N 2 )Sc(H)OH. nScH assignments, based on isotopic shifts and DFT calculations, are listed in Table 1. 1 The FTIR spectrum of Sc 3 N@C 80 gave assignments for two isomers-both with trigonal planar Sc 3 N units. 2 There is IR evidence that ScO + in noble gas matrices forms adducts [ScO(Ng) 5Àn (Ng 0 ) n ] + , where n = 0-5, Ng, Ng 0 = Ar, Kr, Xe. nScO assignments are given in Table 2. 3 Laser-evaporated ScO and N 2 , or Sc atoms and N 2 O form the matrix-trapped species OSc(Z 2 -N 2 ). This rearranges to an Z 1 -form (OScNN) on UV irradiation. nScO for the former is at 906.5 cm À1 , and for the latter at 894.6 cm À1 . 4 The Raman spectrum of [Sc(OSMe 2 ) 6 ] 3+ includes symmetric (a g ) and degenerate (e g ) nScO modes at 429, 451 cm À1 , respectively. The IR spectrum includes bands at 452 and 463 cm À1 due to e u , a u modes, respectively. 5 Ab initio calculations gave skeletal vibrational wavenumbers for Sc(mda) 3 ,where mda = C 3 H 3 O 2 À . 6 Raman studies have revealed grain-size effects for nanocrystalline ZrO 2 -Sc 2 O 3 , i.e. (ZrO 2 ) 1Àx (Sc 2 O 3 ) x , where x = 0.02-0.16. 7 The IR and Raman spectra of M 2 (M 0 O 4 ) 3 , where M = Sc, In, M 0 = Mo, W, gave characteristic assignments. For Sc 2 (MoO 4 ) 3 , variable-temperature spectra show the effects of the ferroelastic phase transition. 8 There have been two other reports of Raman studies of the phase behaviour of Sc 2 (MoO 4 ) 3 . 9,10 Raman spectroscopy was used to characterise intermediate compositions in the systems Ln 2 S 3 -Ln 0 2 S 3 , where Ln = La, Dy, L 0 = Sc, Lu etc. 11 The variable-temperature Raman spectra of Rb 2 KScF 6 (elpasolite) were used to follow temperature-induced phase transitions (using both ScF 6 and lattice modes). 12 The IR spectra of MCl 2 (k 3 -L)(thf), where M = Sc, Y, HL = (1), R = COOH, CSSH and CH 2 OH, include nMS near 300 cm À1 , and nMO (R = CH 2 OH) 570 cm À1 . 13 Characteristic Raman bands were seen at 204 and 42 cm À1 for a superconducting YNi 2 B 2 C single crystal. 14 The IR spectrum of Y 2 O 3 shows that nY-O shifts to lower wavenumber with decreased particle size. 15 Variable-temperature Raman spectroscopy was used to follow phase transitions of Y 2 O 3 -ZrO 2 . 16 IR and Raman spectra gave vibrational wavenumbers for orthorhombic M 2 BaCuO 5 , where M = Y, Ho or Gd, assigned using a short-range force constant model. 17 The Raman spectra of Ln 3 NbO 7 , where Ln = Y, La, Nd, Gd, in the temperature range 298-973K gave evidence for reversible structural disordering on increasing temperature. 18 IR data, together with previous Raman bands, gave assignments for KY 3 F 10 single crystals, supported by a normal coordinate analysis. 19 The IR and Raman spectra of [Ln(OH 2 ) 9 ] 3+ , where Ln = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, gave detailed assignments for the LnO 9 unit (D 3h ). 20 Structural characteristics of MFeGe 2 O 7 , where M...

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Organometallic Molybdenum(V) Complexes with Primary Phosphine Ligands. Syntheses, Spectroscopic Properties and Molecular Structures of [Cp°MoCl₄(PH₂R)] (R = Bu^t, 1‐Ad, Cy, Ph, 2, 4, 6‐Me₃C₆H₂, 2, 4, 6‐Prⁱ₃C₆H₂, Cp° = C₅EtMe₄)

Cited by 16 publications

References 87 publications

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

Rhodium-Catalyzed Isomerization of a Bis(secondary phosphine) to an Unsymmetrical Diphosphine via P–C Cleavage and P–P and C–H Bond Formation

Vibrational spectra of transition element compounds

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