Synthesis and structural aspects of M-allyl (M=Ir, Rh) complexes

Sivaramakrishna, Akella; Hager, Emma; Zheng, Feng; Su, Hong; Smith, Gregory S.; Moss, John R.

doi:10.1016/j.jorganchem.2007.07.053

Cited by 13 publications

(10 citation statements)

References 21 publications

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“…These structures reveal that 1a and 1b adopt distorted piano-stool geometries with capping η 3 -allyl ligands in a similar arrangement to that seen in a range of related complexes. 78,79 The structures are very similar to each other with the Ir-P distances of 1a and 1b being close (see Tables 1 and 2). The increase in electron density resulting from moving from PPh 3 to P(p-tolyl) 3 is insufficient to change the Ir-C(O) bond length in 1a from that in 1b.…”

Section: Introductionsupporting

confidence: 59%

Usingparahydrogen induced polarization to study steps in the hydroformylation reaction

et al. 2019

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Section: Introductionsupporting

confidence: 59%

Usingparahydrogen induced polarization to study steps in the hydroformylation reaction

et al. 2019

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“…We also prepared bis(1‐alkenyl)Pt(II) complexes ( 4 ) by reacting the appropriate Grignard reagents with Pt[COD]Cl 2 , followed by ligand displacement using various phosphine ligands (Scheme ) to obtain the corresponding L 2 Pt(1‐alkenyl) 2 complexes, where L = PPh 3 , t Bu 3 P; L 2 = dppe, dppp; n = 1–4 and 7 ( 5 , 6 , 7 , 8 , 9 , 10 ) . As this route is not limited to platinum, a similar route was employed for the synthesis of a series of bis(1‐alkenyl)Pd(II) complexes L 2 Pd[(CH 2 ) n CHCH 2 ] 2 with varying chain lengths (Scheme ) and also a series of bis(1‐alkenyl)Ir(III) complexes (equation ) …”

Section: Methodsmentioning

confidence: 99%

“…PtCl(dppp)[(CH 2 ) 3 CHCH 2 ] complex ( 37 ) derived from (dppp)PtCl 2 ( 36 ) undergoes an irreversible rearrangement to the η 3 ‐1,3‐dimethylallyl cationic complex ( 38 ) (Scheme ). The new monoalkenyl complex, PtCl(dppp)[(CH 2 ) 3 CH=CH 2 ], thus obtained is sensitive to temperature, solvent and light.…”

Section: Reactivitymentioning

confidence: 99%

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Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Sravani

Venkatesh

Vijayakrishna

et al. 2014

Applied Organom Chemis

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Intermediates for many catalysis reactions reported in the literature are metal‐alkyl and metal‐alkenyl, including metallacycloalkane species. Synthesis and reactions of metal‐alkyl, alkenyl and metallacyle complexes have shown a great deal of development during the past few decades. This review summarizes the significant contributions reported on metal‐alkenyl compounds, specifically those containing at least a carbon chain with pendant alkene group [M―CH2CH2CHCH2]. Although metal‐alkenyl complexes are stable with strong chelating diphosphines and with a decrease in the ligand donor strength, the complexes can decompose without any ambiguity. For example, platinum‐dialkenyl complexes react readily via β‐hydrogen elimination and reductive elimination promoted by the nature of the ligand, solvent and length of carbon chains. These complexes can also undergo intramolecular irreversible isomerization and this leads to the selective catalytic isomerization of 1‐alkenes to 2‐alkenes in the presence of platinum‐dialkenyl complexes as catalysts. Perhaps the most striking manifestations of flexibility are the facile and complete intramolecular and intermolecular alkene metathesis to yield the corresponding metallacycloalkenes in the presence of Grubbs’ catalysts. The diverse chemical reactivity of these complexes demonstrates both the scope and complexity of metal‐alkenyl chemistry depending on the nature of ligand and metal. Copyright © 2014 John Wiley & Sons, Ltd.

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“…The cyclopentadienyl and its substituted ligands have become one of the most extensively utilized ligands in organometallic chemistry. [1][2][3] Cyclopentadienyl (Cp), 4-9 methylcyclopentadienyl (MeCp), 10,11 tetramethylcyclopentadienyl (Me 4 Cp) 12 and pentamethylcyclopentadienyl (Me 5 Cp) 13,14 coordinated to Co, [4][5][6][7][8][9][12][13][14] Rh 7,8,11,14 and Ir [8][9][10] to form different compounds have been well documented. On the other hand, Cp, t Bu 2 Cp,15 Me 5 Cp and the neutral 6-electron ( p-cymene) ring combine with the bulky chelating 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligand, [E 2 C 2 B 10 H 10 ] 2− (E = S, Se) to construct 16-electron halfsandwich Co, Rh, Ir, Ru and Os complexes Cp # M(E 2 C 2 B 10 H 10 ) (Cp # = Cp, t Bu 2 Cp, Me 5 Cp; M = Co, Rh, Ir; E = S, Se) and ( p-cymene)M(S 2 C 2 B 10 H 10 ) (M = Ru, Os).…”

Section: Introductionmentioning

confidence: 99%

Reactivity of 16-electron half-sandwich cobalt compounds containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards methyl propiolate and dithio ligands

Zhang

Zhu

et al. 2012

Dalton Trans.

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The reaction of the 16-electron half-sandwich complex MeCpCo(S2C2B10H10) (1b; MeCp = methylcyclopentadienyl) and methyl propiolate (HC≡CCO2Me) at ambient temperature leads to MeCpCo(S2C2B10H9)(CH=CHCO2Me) (2), MeCpCo(S2C2B10H8)(CH=CHCO2Me)2 (3), MeCpCo-(S2C2B10H9)[MeO2CC=CH(MeO2C)C=CH)](CH=CHCO2Me) (4) and MeCpCo(S2C2B10H9)-(CH2CCO2Me) (5). The reaction of Me4CpCo(S2C2B10H10) (1c; Me4Cp = tetramethylcyclopentadienyl) and the alkyne gives rise to Me4CpCo(S2C2B10H10)[MeO2CC=CH(MeO2C)C=CH] (6) and Me4CpCo(S2C2B10H9)(CH2CCO2Me) (7). Both 2 and 3 are 16-electron complexes but containing a B(3)-substituted o-carborane-1,2-dithiolate ligand in 2 and a B(3,6)-disubstituted o-carborane-1,2-dithiolate ligand in 3, respectively. In 4 and 6, two alkynes are inserted into one Co–S bond to meet an 18 electron configuration at metal, however, 4 has one B-substitution at carborane. Both 5 and 7 have the same structural type bearing a B–CH2 unit. The reactions of Cp#Co(E2C2B10H10) [Cp# = Cp (1a), MeCp (1b), Me4Cp (1c) and Me5Cp (1d); E = S, Se] with 2-methylpropanedithioic acid (L1) or pyrrolidine-1-carbodithioic acid (L2) lead to Co[S2CCH(CH3)2]3 (8) or Co[S2CN(CH2)4]3 (9), respectively, in an octahedral geometry. The three-component reactions of 1a–1d, methyl propiolate and L1 or L2 afford seven new compounds Cp#Co[S2C2B10H10(CH=CHCO2Me)][S2CCH(CH3)2] [Cp# = Cp (10a), MeCp (10b) and Me4Cp (10c)], [S2CCH(CH3)2]2Co(S2C2B10H10)(CH=CCO2Me){CpCo[S2CCH(CH3)2]} (11a), Cp#Co[S2C2B10H10(CH=CHCO2Me)][S2CN(CH2)4] [Cp# = Cp (12a), MeCp (12b) and Me4Cp (12c)]. All 10a–10c and 12a–12c contain one deprotonated L1 or L2 ligand and one reduced alkyne. 11a has two 18-electron Co centers linked by one reduced alkyne. One metal is coordinated by an o-carborane-1,2-dithiolate and two L1 ligands, and the other is coordinated by one L1 ligand and one η5-Cp unit. In both two- and three-component reactions the reactivity of the 16-electron half-sandwich complexes Cp#Co(S2C2B10H10) is dependent on the size of the Cp# unit. All compounds were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 4, 5, 7, 10a and 11a were further determined by X-ray crystallographic analysis.

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Synthesis and structural aspects of M-allyl (M=Ir, Rh) complexes

Cited by 13 publications

References 21 publications

Usingparahydrogen induced polarization to study steps in the hydroformylation reaction

Usingparahydrogen induced polarization to study steps in the hydroformylation reaction

Alkenyl complexes of platinum group metals: a platform for diverse reactivity patterns

Reactivity of 16-electron half-sandwich cobalt compounds containing a chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligand towards methyl propiolate and dithio ligands

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