Synthesis, Structure, and Deprotonation of a Mesitylphosphido-Bridged Cyclopentadienylnickel(II) Dimer

Maslennikov, S. V.; Glueck, David S.; Yap, Glenn P. A.; Rheingold, Arnold L.

doi:10.1021/om950982u

Cited by 21 publications

(10 citation statements)

References 17 publications

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“…The observed bond lengths of the P 2 Ni 2 ring fit well to those found in the analogous phosphido bridged dinuclear NiCp-complexes, [CpNi(PHMes)] 2 (NiϪP 215.2 pm, NiϪNi 334.1 pm) [21] and [CpNi(PPh 2 )] 2 (NiϪP 215.6 pm, NiϪNi 335.7 pm) [22] as well as in the tetramethylphospholyl complex [(η 5 -C 4 Me 4 P)Ni(µ-C 4 Me 4 P)] 2 (NiϪP 217.1 pm, NiϪNi 334.0 pm) [23]. Suitable crystals were obtained from a cooled (ϩ5°C) solution in THF containing C 6 H 6 .…”

Section: Crystal and Molecular Structure Of 6e · 2 C 6 Hsupporting

confidence: 78%

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Heinicke

Gupta

Singh

et al. 2002

Z. anorg. allg. Chem.

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1H-1,3-Benzazaphospholes react with M(CO) 5 (THF) (M ϭ Cr, Mo, W) to give thermally and relatively air stable η 1 -(1H-1,3-Benzazaphosphole-P)M(CO) 5 complexes. The 1 H-and 13 C-NMR-data are in accordance with the preservation of the phosphaaromatic π-system of the ligand. The strong upfield 31 P coordination shift, particularly of the Mo and W complexes, forms a contrast to the downfield-shifts of phosphine-M(CO) 5 complexes and classifies benzazaphospholes as weak donor but efficient acceptor ligands. Nickelocene reacts as organometallic species with metalation of the NH-function. The resulting ambident 1,3-benzazaphospholide anions prefer a µ 2 -coordination of the η 5 -CpNi- Metallierte 1,3-Azaphosphole: η 1 -(1H-1,3-Benzazaphosphol-P)M(CO) 5 und µ 2 -[(1,3-Benzazaphospholid-P)(cyclopentadienid)nickel] KomplexeInhaltsübersicht.1H-1,3-Benzazaphosphole reagieren mit M(CO) 5 (THF) (M ϭ Cr, Mo, W) zu thermisch und zumindest kurzzeitig luftstabilen η 1 -(1H-1,3-Benzazaphosphol-P)M(CO) 5 -Komplexen. Die 1 H-und 13 C-NMR-Daten sind mit dem Erhalt des phosphaaromatischen π-Systems im Liganden im Einklang. Die starke 31 P-Koordinationsverschiebung zu hohem Feld, vor allem der Mo-und W-Komplexe, steht im Gegensatz zur Koordinationsverschiebung zu tiefem Feld, beobachtet bei Phosphin-M(CO) 5 Komplexen, und verweist auf schwache Donator-, aber gute Akzeptoreigenschaften der Liganden. Nickelocen reagiert als Übergangsmetallorganyl unter Metallierung der NH-Funktion.

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Section: Crystal and Molecular Structure Of 6e · 2 C 6 Hsupporting

confidence: 78%

Untitled

Heinicke

Gupta

Singh

et al. 2002

Z. anorg. allg. Chem.

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“…Several papers by the groups of Haupt [33], Scheer [34], Whitmire [35], Glueck [36] and Mays [37] also dealt with deprotonation of PHR-bridged dinuclear complexes which, as judged from trapping experiments with halocomplexes or other electrophiles, led to the formation of intermediate anionic phosphinidene complexes. However, most of these intermediates were poorly characterised and unstable species for which even their solution structures could not be defined clearly.…”

Section: Scheme 12mentioning

confidence: 99%

“…The protonation reaction of the lithium salt of the dianionic bis(phosphinidene) complex and anti isomers (R = H), or only as the syn isomer (R = Me) [36]. Likewise, the diplatinum phosphinidene complex 30, also generated in situ, reacted with excess MeI to form the phosphanyl dication 76, whereas the addition of excess BH 3 ·THF led to the borane adduct 77 (Scheme 41) [41].…”

Section: Reactions With Simple Electrophilesmentioning

confidence: 99%

Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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This article contains a comprehensive review of the work carried out within the last three decades on the synthesis, structural studies and reactivity of the binuclear complexes of transition and lanthanide elements bearing bridging phosphinidene (PR) ligands. The latter are grouped into three different classes according to their geometry and electronic distribution: pyramidal, symmetric planar trigonal and asymmetric planar trigonal. Different reactivity patterns can be then outlined for each of these classes of metal complexes, which differ in many ways from those characterizing the extensively studied chemical behaviour of mononuclear phosphinidene complexes.

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“…For example, the signal due to the mesitylphosphinidene ligand in C 5 R 5 W(CO) 2 (μ-PMes)C 5 R 5 W(CO) 2 (PH 2 Mes) appears at δ 313.9 (R = H) and 397.4 (R = Me), while for [Cp*W(CO) 2 ] 2 (μ-PMes) this resonance is observed at δ 589.4 . The chemical shift of the μ-phosphinidene ligand in 1 , δ −56.8, is more similar to that of Li 2 [NiCp(μ-PMes)] 2 (δ 13.8), consistent with a lack of multiple bonding in these cases and disfavoring structure 1a .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

Kourkine

Glueck

1997

Inorg. Chem.

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The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]2 (1; dppe = Ph2PCH2CH2PPh2, Mes = 2,4,6-Me3C6H2) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]2[BF4]2 (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}2(μ-PHMes)(μ-PMes)][BF4] (2), which can also be made from 1 and 1 equiv of HBF4. NMR data suggest that complex 1 contains pyramidal μ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){μ-P(Me)Mes}]2[BF4]2 (4), BH3·THF gives the borane adduct [Pt(dppe){μ-P(BH3)Mes}]2 (5), and air oxidation yields [Pt(dppe){μ-P(O)Mes}]2 (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S3PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS2]2.

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Synthesis, Structure, and Deprotonation of a Mesitylphosphido-Bridged Cyclopentadienylnickel(II) Dimer

Cited by 21 publications

References 17 publications

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Phosphinidene-bridged binuclear complexes

Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

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