Synthesis of [Mo2{μ-Au(PPh3)}Cp2(CO)4(μ-PPh2)] and structural comparison with the dimolybdenum complexes [Mo2Cp2(CO)4(μ-H)(μ-PPh2)] and PPN[Mo2Cp2(CO)4(μ-PPh2)] (PPN = (PPh3)2N+)

Hartung, H.; Walther, B.; Baumeister, Ute; Böttcher, Hans‐Christian; Krug, A.; Rosche, Fred; Jones, Peter G.

doi:10.1016/s0277-5387(00)83707-9

Cited by 29 publications

(26 citation statements)

References 9 publications

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“…These intermetallic lengths are comparable to the average value found for the related electron-precise trinuclear cluster [AuMo 2 Cp 2 (l-PPh 2 )(CO) 4 (PPh 3 )], although the asymmetry of the bridging AuPPh 3 moiety in that molecule is much higher, with the MoÀAu lengths differing by ca. 0.2 Å [21]. Finally, we note that the AuÀAu distance of 2.7832(2) Å in 7b falls in the short side of the range usually found in heterometallic clusters containing gold(I)Àgold(I) bonding interactions (2.70-3.10 Å) [17].…”

Section: Structural Characterization Of Compounds 7absupporting

confidence: 50%

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Alvarez

Garcı́a

Ramos

et al. 2010

Journal of Organometallic Chemistry

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Section: Structural Characterization Of Compounds 7absupporting

confidence: 50%

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Alvarez

Garcı́a

Ramos

et al. 2010

Journal of Organometallic Chemistry

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“…This interaction is most clearly evidenced by the anomalous 13 C chemical shifts of the ipso (116.2 ppm) and ortho (168.3 ppm) atoms of the Ph group, which are more shielded and deshielded, respectively, than those values typically observed for conventional phenyl ligands in either terminal or bridging complexes. In the same line, the 31 12 than to the corresponding figure in the 30-electron hydride 2B (167.2 ppm).…”

Section: Chartmentioning

confidence: 69%

Hydride, gold(i) and related derivatives of the unsaturated ditungsten anion [W₂Cp₂(μ-PCy₂)(μ-CO)₂]⁻

et al. 2014

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ARTICLEThis journal is © The Royal Society of Chemistry 2013 J. Name., 2013, 00, 1-3 | 1 12 in stark contrast with the exclusive bridging disposition found for its dimolybdenum analogue. 9 Then, it was of interest to further explore the potential of ditungsten anion 1 to build new unsaturated hydrides and related species, which is the main purpose of this work. In this paper we give full details of the protonation reactions of 1, which we have now extended to other Brönsted acids and also to H + -related electrophiles such as gold(I) complexes [AuCl(PR 3 )] and organometal chlorides ClEPh 3 (E = Sn, Pb). As it will be shown below, most of these reactions involve the addition of the corresponding electrophile at the dimetal site of the anion, to give new unsaturated compounds related to those obtained for the dimolybdenum analogue of 1. In contrast, only the ditungsten anion 1 is able to undergo double protonation to give stable dihydride derivatives, which are relatively stable towards dehydrogenation in the absence of coordinating anions. Scheme 1 Results and Discussion Protonation of compounds 1 and 2The sodium salt of anion 1 is easily protonated in tetrahydrofuran solution by weak acids such as [NH 4 and another one bearing only terminal hydrides [W 2 Cp 2 (H) 2 (-PCy 2 )(CO) 2 ]X (3T and 3T')] (Scheme 2). These isomers seem to be also in equilibrium in solution, and a ratio of ca. 6:5 was found in both cases. Unfortunately, these species could not be isolated as pure solids and decomposed progressively upon attempted purification, but their structures are well supported by spectroscopic data and DFT calculations (see below). In any case we note that the nature of the metal (W instead of Mo) is having a critical role in the stability of these products, because protonation of the Mo 2 analogue of 2 fails to yield any observable dihydrides and leads instead to complex mixtures of products that could not be isolated or characterized. Scheme 2To gain further insight into the role of the external anion in these reactions, we also examined reactions of 2 with some acids having coordinating anions. In particular, we have used three carboxylic acids of increasing acidity: acetic, benzoic and trifluoroacetic acid. No reaction was observed for the weaker acetic acid, but reaction of 2 with a slight excess of benzoic or trifluoroacetic acid gave the corresponding carboxylate-bridged complexes [W 2 Cp 2 (-PCy 2 )(-O:O´-O 2 CR)(CO) 2 ] [R = Ph(4a), CF 3 (4b)] (Chart 1), with the latter reaction taking place instantaneously at room temperature, while the former one requires thermal activation (completed within 30 min in refluxing toluene). There are two points of interest in these reactions: first, their rates correlate with the relative strength of these acids (CF 3 CO 2 H >> PhCO 2 H > CH 3 CO 2 H), which suggests that initial protonation to give cations analogous to 3 might be the first step of the process; secondly, the formation of the carboxylate complexes 4a,b requires release of hydrogen, likely occurring at...

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“…Indeed, these complexes share almost the same 31 [27], cationic gold fragments can be added to electron-rich complexes having metalmetal bonds to give heterometallic derivatives alike to the corresponding hydride complexes following from protonation [28]. Since dicarbonyl 2 is nucleophilic enough to be protonated [5], it could be anticipated that it should be able to add gold(I) cations, although the output of these reactions proved to be different from protonation.…”

Section: Chartmentioning

confidence: 99%

“…The minor isomer displays a PCy 2 resonance at 223.8 ppm, a position almost identical to those of compounds 8b,c, and is thus assigned to the isomer syn. The major isomer of 8a, identified by a slightly more shielded 31 3 }]PF 6 a molecule proposed to be formed through initial attack of the gold electrophile to the Mo-P bond of the parent carbyne complex [8]. This exemplifies the great influence that subtle electronic and steric factors exert over the course of these cluster-building reactions.…”

Section: Structure Of the Cis Complexesmentioning

confidence: 99%

Heterometallic clusters derived from the unsaturated carbyne-bridged dimolybdenum complexes [Mo 2 (η 5 -C 5 H 5 ) 2 (μ-CPh) (μ-PCy 2 ) (CO) x ] (x = 1, 2)

Alvarez

Garcı́a

Menéndez

et al. 2015

Journal of Organometallic Chemistry

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Synthesis of [Mo2{μ-Au(PPh3)}Cp2(CO)4(μ-PPh2)] and structural comparison with the dimolybdenum complexes [Mo2Cp2(CO)4(μ-H)(μ-PPh2)] and PPN[Mo2Cp2(CO)4(μ-PPh2)] (PPN = (PPh3)2N+)

Cited by 29 publications

References 9 publications

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Hydride, gold(i) and related derivatives of the unsaturated ditungsten anion [W₂Cp₂(μ-PCy₂)(μ-CO)₂]⁻

Heterometallic clusters derived from the unsaturated carbyne-bridged dimolybdenum complexes [Mo 2 (η 5 -C 5 H 5 ) 2 (μ-CPh) (μ-PCy 2 ) (CO) x ] (x = 1, 2)

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Synthesis of [Mo2{μ-Au(PPh3)}Cp2(CO)4(μ-PPh2)] and structural comparison with the dimolybdenum complexes [Mo2Cp2(CO)4(μ-H)(μ-PPh2)] and PPN[Mo2Cp2(CO)4(μ-PPh2)] (PPN = (PPh3)2N+)

Cited by 29 publications

References 9 publications

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Reactivity of the unsaturated dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards electrophiles based on p- and d-block elements

Hydride, gold(i) and related derivatives of the unsaturated ditungsten anion [W2Cp2(μ-PCy2)(μ-CO)2]−

Heterometallic clusters derived from the unsaturated carbyne-bridged dimolybdenum complexes [Mo 2 (η 5 -C 5 H 5 ) 2 (μ-CPh) (μ-PCy 2 ) (CO) x ] (x = 1, 2)

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Hydride, gold(i) and related derivatives of the unsaturated ditungsten anion [W₂Cp₂(μ-PCy₂)(μ-CO)₂]⁻