Carbamoyl Complexes of Divalent Tungsten, Molybdenum, and Iron and the Unexpected Formation of an Aminomethylidyne Complex

Anderson, Sharolyn; Cook, Darren J.; Hill, Anthony F.

doi:10.1021/om970738y

Cited by 26 publications

(22 citation statements)

References 13 publications

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“…The red‐brown arylamido complexes 2 a (Ar=Ph) and 2 b (Ar= p ‐tolyl), obtained as single products, could be isolated in good yield after a simple workup procedure (see Experimental Section). The 1 H NMR spectra of 2 a – b showed the presence of an intact η 3 ‐methallyl group, confirming that the metal, and neither the allyl ligand nor the carbonyls,17 has been the site of the amide attack, in line with our recent results employing alkyl,18 alkoxide,13b or hydroxide13c nucleophiles toward molybdenum chloro complexes such as 1 . Broad, one‐hydrogen singlets at δ =3.88 ( 2 a ) and 3.90 ppm ( 2 b ) in CD 2 Cl 2 were assigned to the nitrogen‐bonded hydrogen of the amido ligands 19.…”

Section: Resultssupporting

confidence: 86%

Molybdenum Amido Complexes with Single MoN Bonds: Synthesis, Structure, and Reactivity

Morales

Pérez

Riera

et al. 2003

Chemistry A European J

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Reactions of the complex [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (phen=1,10-phenanthroline) with potassium arylamides were used to synthesize the amido complexes [Mo(N(R)Ar)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (R=H, Ar=Ph, 2 a; R=H, Ar=p-tolyl, 2 b; R=Me, Ar=Ph; 2 c). For 2 b the Mo-N(amido) bond length (2.105(4) A) is consistent with it being a single bond, with which the metal attains an 18-electron configuration. The reaction of 2 b with HOTf affords the amino complex [Mo(eta(3)-C(3)H(4)-Me-2)(NH(2)(p-tol))(CO)(2)(phen)]OTf (3-OTf). Treatment of 3-OTf with nBuLi or KN(SiMe(3))(2) regenerates 2 b. The new amido complexes react with CS(2), arylisothiocyanates and maleic anhydride. A single product corresponding to the formal insertion of the electrophile into the Mo-N(amido) bond is obtained in each case. For maleic anhydride, ring opening accompanied the formation of the insertion product. The reaction of 2 b with maleimide affords [Mo(eta(3)-C(3)H(4)-Me-2)[NC(O)CH=CHC(O)](CO)(2)(phen)] (7), which results from simple acid-base metathesis. The reaction of 2 b with (p-tol)NCO affords [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(eta(2)-MoO(4))] (8), which corresponds to oxidation of one third of the metal atoms to Mo(VI). Complex 8 was also obtained in the reactions of 2 b with CO(2) or the lactide 3,6-dimethyl-1,4-dioxane-2,5-dione. The structures of the compounds 2 b, 3-OTf, [Mo(eta(3)-C(3)H(4)-Me-2)[SC(S)(N(H)Ph)](CO)(2)(phen)] (4), [Mo(eta(3)-C(3)H(4)-Me-2)[SC(N(p-tol))(NH(p-tol))](CO)(2)(phen)] (5 a), and [Mo(eta(3)-C(3)H(4)-Me-2)[OC(O)CH=CHC(O)(NH(p-tol))](CO)(2)(phen)] (6), 7, and 8 (both the free complex and its N,N'-di(p-tolyl)urea adduct) were determined by X-ray diffraction.

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Section: Resultssupporting

confidence: 86%

Molybdenum Amido Complexes with Single MoN Bonds: Synthesis, Structure, and Reactivity

Morales

Pérez

Riera

et al. 2003

Chemistry A European J

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“…19 Binuclear chalcoacyl complexes, however all adopt a dimetallachalcotetrahedrane geometry in which the CE (E = S, Se, Te) group transversely bridges a metal-metal bond (Chart 1), 20 with the exception of [MRu(µ-SCC 6 H 4 Me-4)(CO) 4 (η 5 -C 2 B 9 H 9 Me 2 )(Tp)] (Chart 1e; Tp = hydrotris(pyrazol-1-yl)borate). 21 The spectroscopic data for 3, whilst indicating a binuclear complex of low symetry, did not allow for unequivocal identification, not least because the small range of 13 C NMR data reported for thioacyl groups 18 overlaps somewhat with the wide range observed for alkyidyne ligands (vide infra, Table 1 18,19, [22][23][24][25][26][27][28] ). 17 The formulation was however confirmed by a crystallographic analysis, the results of which are summarised in Figure 1.…”

Section: Scheme 2 Alternative Syntheses Of a Thioxoethenylidene Compmentioning

confidence: 99%

Thioxoethenylidene (CCS) as a Bridging Ligand

et al. 2014

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The reaction of [Mo(≡CBr)(CO) 2 (Tp*)] (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [Fe 2 (µ-SLi) 2 (CO) 6 ] affords, inter alia, the unsymmetrical binuclear thioxoethenylidene complex [Mo 2 (µ:σ-C;η 2-C'S-CCS)(CO) 4 (Tp*) 2 ] which may be more directly obtained from [Mo(≡CBr)(CO) 2 (Tp*)] and Li 2 S. The reaction presumably proceeds via the intermediacy of the bis(alkylidynyl)thioether complex S{C≡Mo(CO) 2 (Tp*)} 2 which was, however, not directly observed but explored computationally and found to lie 78.6 kJ mol-1 higher in energy than the final thioxoethenylidene product. Computational interrogation of the molecules [M 2 (µ-C 2 S)(CO) 2 (Tp*) 2 ] (M = Mo, W, Re, Os) reveals three plausible coordination modes for a thioxoethenylidene bridge which involve a progressive strengthening of the CC bond and weakening of the M-C and M-S bonds, as might be expected from simple effective atomic number considerations. Scheme 1. Generation and Electrophilic Quenching of a Binuclear Alkynylthiolato Complex. 16

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“…Some recent examples are: CpW[CH@CH(t-Bu)](NO)(g 2 -CONR 2 ) [8], M(g 2 -CON i Pr 2 )I(CO) 3 (PPh 3 ) M = Mo, W, [9] Pt(Cl)(CON-HR)(PPh 3 ) 2 [10], Fe[CON i Pr 2 ] 2 (CO) 4 [11], (PN)PdCl(CONHC 6 H 4 OH) [2] and [Fe(g 2 -OCNi-Pr 2 )(X)(CO) 2 (PPh 3 )] (X = Br, I) [12]. Rare examples of carbamoyl complexes are those were the carbamoyl ligand is part of a side chain of a cyclopentadienyl group coordinated to a same metal fragment.…”

Section: Introductionmentioning

confidence: 99%

Reactions of cationic complex [(η5-C5Me5)Re(CO)3I]+ with primary amines leading to cyclic carbamoyl complexes

Aballay

Buono-Core

Godoy

et al. 2009

Journal of Organometallic Chemistry

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Carbamoyl Complexes of Divalent Tungsten, Molybdenum, and Iron and the Unexpected Formation of an Aminomethylidyne Complex

Cited by 26 publications

References 13 publications

Molybdenum Amido Complexes with Single MoN Bonds: Synthesis, Structure, and Reactivity

Molybdenum Amido Complexes with Single MoN Bonds: Synthesis, Structure, and Reactivity

Thioxoethenylidene (CCS) as a Bridging Ligand

Reactions of cationic complex [(η5-C5Me5)Re(CO)3I]+ with primary amines leading to cyclic carbamoyl complexes

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