Synthesis and reactions of the cyclooctadienylmolybdenum complexes [MoBr(CO)2(NCMe)2(η3-C8H11)] (η3-C8H11 = 1–3-η:4,5-C8H11 or 1–3-η:5,6-C8H11)

Spencer, Dale M.; Beddoes, Roy L.; Dissanayake, Rasika K.; Helliwell, Madeleine; Whiteley, Mark W.

doi:10.1039/b107581k

Cited by 4 publications

(5 citation statements)

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“…The synthetic route that we developed to cyclooctadienyl molybdenum complexes [5] is closely paralleled in the corresponding tungsten chemistry. Thus reaction of acetonitrile solutions of [W(CO) 3 (NCR) 3 ] (R ¼ Me or Pr n ) with mixtures of either 3-Br-1,5-cod/6-Br-1,4-cod or 5-Br-1,3-cod/3-Br-1,4-cod (cod ¼ cyclooctadiene) led, respectively, to the formation and precipitation of [WBr (CO) 2 (NCMe) 2 (1-3-g:5,6-C 8 H 11 )] (6) and [WBr (CO) 2 (NCMe) 2 (1-3-g:4,5-C 8 H 11 )] (7).…”

Section: Cyclooctadienyl Complexesmentioning

confidence: 98%

“…Microanalytical, infrared and mass spectroscopic data for each of the complexes are presented in Table 1, and 1 H, 13 C{ 1 H} and 31 P{ 1 H} NMR data are given in Table 2. Again, a full account of the spectroscopic data for analogous molybdenum complexes has been presented previously [5,6] and, therefore, further discussion here is restricted. Both commonly observed forms of the cyclooctadienyl ligand are included in this study.…”

Section: Cyclooctadienyl Complexesmentioning

confidence: 99%

“…Edge-bridged dienyl ligands are of interest because of the structural effects of the edge bridge and their ability to coordinate to a metal centre both as g 5 and g 3 ligands with interconversion between the two hapticity types in selected examples [1,2]. The focus of our work in this area to date has been with cycloheptadienyl [3,4] and cyclooctadienyl [5,6] complexes of molybdenum but in the current paper we extend our investigations to the chemistry of the analogous tungsten systems. It is not our intention to provide a comprehensive and exhaustive account of cycloheptadienyl and cyclooctadienyl tungsten chemistry but rather our objectives are (i) to describe synthetic routes to the tungsten complexes and (ii) to highlight differences in reactivity resulting from exchange of molybdenum for tungsten especially with respect to g 5 !…”

Section: Introductionmentioning

confidence: 94%

“…Elution with CH 2 Cl 2 /acetone (1:1) gave a yellow band followed by an orange band, which was collected and evaporated to dryness. The residue, tentatively formulated as [W(CO) 3 (dppm-P 0 )(g 5 W(CO) 6 (4.15 g, 11.79 mmol) was refluxed in NCMe (50 cm 3 ) for 4 days after which time a yellow solution of [W(CO) 3 (NCMe) 3 ] had formed. This was cooled to room temperature and a mixture of 3-Br-1,5-cod and 6-Br-1,4-cod (2.30 g, 12.30 mmol) added, resulting in an orange solution.…”

Section: Preparation Of [W(co) 2 (Dppm)(g 5 -C 7 H 9 )][Bf 4 ] (5)mentioning

confidence: 99%

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Synthesis and reactions of cycloheptadienyl and cyclooctadienyl tungsten complexes: X-ray crystal structure of [W(CO)2(PPh3)2(η5-C7H9)][BF4]

Carruthers

Helliwell

Hinchliffe

et al. 2004

Journal of Organometallic Chemistry

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Section: Cyclooctadienyl Complexesmentioning

confidence: 98%

Section: Cyclooctadienyl Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 94%

Section: Preparation Of [W(co) 2 (Dppm)(g 5 -C 7 H 9 )][Bf 4 ] (5)mentioning

confidence: 99%

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Synthesis and reactions of cycloheptadienyl and cyclooctadienyl tungsten complexes: X-ray crystal structure of [W(CO)2(PPh3)2(η5-C7H9)][BF4]

Carruthers

Helliwell

Hinchliffe

et al. 2004

Journal of Organometallic Chemistry

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“…However, this does not preclude a concerted pathway via TS1, see Sections 2.1 and 3.1. Further work is needed to explain the low yields for many complexes with cyclic allylic ligands, [8,132,156] and afford some insight on the potential of these complexes to effect various C-X, C-H or C-C bond activations, which delineate a duality with the concerted mechanism of oxidative addition.…”

Section: Mechanistic Features Structural Aspects and Dynamic Behaviourmentioning

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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Molybdenum Compounds with CO or Isocyanides

Tamm

Baker

2007

Comprehensive Organometallic Chemistry III

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Synthesis and reactions of the cyclooctadienylmolybdenum complexes [MoBr(CO)2(NCMe)2(η3-C8H11)] (η3-C8H11 = 1–3-η:4,5-C8H11 or 1–3-η:5,6-C8H11)

Cited by 4 publications

References 31 publications

Synthesis and reactions of cycloheptadienyl and cyclooctadienyl tungsten complexes: X-ray crystal structure of [W(CO)2(PPh3)2(η5-C7H9)][BF4]

Synthesis and reactions of cycloheptadienyl and cyclooctadienyl tungsten complexes: X-ray crystal structure of [W(CO)2(PPh3)2(η5-C7H9)][BF4]

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

Molybdenum Compounds with CO or Isocyanides

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