Reactivity of the labile complex [MoCl(η3-allyl)(CO)2(NCMe)2] with diphosphanes

Pérez, Julio; Morales, Dadonim Vila; Rodríguez, Amor; García-Granda, Santiago

doi:10.1039/b300350g

Cited by 7 publications

(2 citation statements)

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“…This configuration spreads the S-Mo-S bond angle adjacent to thiomethyl groups oriented toward each other [S2-Mo-S3 = 89.03(1) Å]. [48,49] as evidenced by 1 H NMR spectroscopy and mass spectrometry (Scheme 3). Low solubility of 4 in hot hexane enables to isolate the RTt complex 3 in pure form.…”

Section: Resultsmentioning

confidence: 97%

Molybdenum complexes of poly[(methylthio)methyl]borates

et al. 2018

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Section: Resultsmentioning

confidence: 97%

Molybdenum complexes of poly[(methylthio)methyl]borates

et al. 2018

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“…[23,243,244] The crystal structure of the cationic analogue [Mo(CO)2(η 3allyl)(dmpm)(MeCN)] + reveals a most unusual bent carbonyl ligand. [213] A non-innocent behaviour involving electron transfer from the counterion, which takes the form of complex 49, or dinucleation through a μ2-carbonyl, could be the cause for this appearance. The carbonyl ligand hence assumes a bent geometry, avoiding a 19 valence electron metal centre.…”

Section: Scheme 22mentioning

confidence: 99%

η3-Allyl carbonyl complexes of group 6 metals: Structural aspects, isomerism, dynamic behaviour and reactivity

Ryan

Cardin

Hartl

2017

Coordination Chemistry Reviews

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Contents 1. Introduction 2. Complexes [CpM(CO)2(η 3 -allyl)] and related compounds 2.1. Synthetic strategies 2.2. Exo ⇌ endo isomerism 2.3. 95 Mo and 183 W NMR spectroscopy 2.4. Oxidized cationic complexes -reactivity, fluxionality, structural features 2.5. Mixed nitrosyl carbonyl complexes [CpM(CO)(NO)(η 3 -allyl)] + (M = Mo, W) 3. Complexes [M(CO)2(η 3 -allyl)(α-diimine)X] (X = anionic monodentate ligand) and related compounds 3.1. Synthetic strategies 3.2. Mechanistic features, structural aspects, and dynamic behaviour 3.3. Monodentate ligands bound to M(CO)2(η 3 -allyl)(L⏜L): reactivity and intermediacy in allylic alkylations 3.4. Redox Properties and Electrocatalysis 4. Amidinato and pyrazolato complexes related to [M(CO)2(η 3 -allyl)(α-diimine)X] 4.1. Synthesis and dynamic behaviour 4.2. Coordinatively unsaturated species and their reactivity 5. Summary and outlook Acknowledgement References 2 ABSTRACTTransition metal complexes with π-allylic ligands remain an attractive topic in organometallic chemistry, given the numerous reports of a wide variety of synthetic routes, dynamic behaviour and reactivity, structural (including isomerism), spectroscopic and redox properties, and applications in organic synthesis and catalysis. Surprisingly, despite the considerable interest in the rich and varied chemistry of this family of organometallic compounds, there is no recent review. This review is focused on π-allylic representatives of low-cost Group-6 metals bearing one or more carbonyl ligand, the coordination sphere being complemented with η 5cyclopentadienyl (Section 2), chelating ligands, including redox active α-diimines and various complementary diphosphine (Section 3) and novel anionic amidinate or pyrazolate (Section 4) ligands. In Section 1 particular attention is paid to rearrangements of the π-allylic ligand, namely exo and endo isomerism, interconversion mechanisms, fluxionality, and agostic interactions. In addition, the application of multinuclear NMR spectroscopy to the elucidation of such isomerism, and the effect of the metal centre oxidation state on the bonding, dynamic behaviour and reactivity of the π-allylic ligand are described. The detailed mechanistic description of the synthetic routes and dynamic behaviour of selected representatives of αdiimine complexes in Section 2 is followed by a description of the [M(CO)2(η 3 -allyl-H,R)(αdiimine)] 0/+ fragment as a convenient scaffold for diverse monodentate ligands participating in a range of substitution, insertion, intramolecular migration and C-C coupling reactionsfrequently involving also the π-allylic ligand, such as allylic alkylation. Special attention is devoted to selected examples of redox and acid-base reactivity of the α-diimine complexes with emphasis on prospects in electrocatalysis. The amidinate (and related pyrazolate) ligands treated in Section 4 may directly replace the π-allylic ligand in some cyclopentadienyl complexes (Section 2) or the α-diimine ligand in some dicarbonyl π-allylic complexes (Section 3). The brief description...

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Combinatorial Synthesis of Bimetallic Complexes with Three Halogeno Bridges

Gauthier

Québatte

Scopelliti

et al. 2004

Chemistry A European J

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Methods for the synthesis of bimetallic complexes in which two different metal fragments are connected by three chloro or bromo bridges are reported. The reactions are general, fast, and give rise to structurally defined products in quantitative yields. Therefore, they are ideally suited for generating a library of homo- and heterobimetallic complexes in a combinatorial fashion. This is of special interest for applications in homogeneous catalysis. Selected members of this library were synthesized and comprehensively characterized; single-crystal X-ray analyses were performed for 15 new bimetallic compounds.

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Reactivity of the labile complex [MoCl(η3-allyl)(CO)2(NCMe)2] with diphosphanes

Cited by 7 publications

References 9 publications

Molybdenum complexes of poly[(methylthio)methyl]borates

Molybdenum complexes of poly[(methylthio)methyl]borates

η3-Allyl carbonyl complexes of group 6 metals: Structural aspects, isomerism, dynamic behaviour and reactivity

Combinatorial Synthesis of Bimetallic Complexes with Three Halogeno Bridges

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