A CH‐Carbene Complex of Iron by Metal‐Induced Fragmentation of Two Bonds of a Bicyclopentane Unit

Aumann, Rudolf; Wörmann, Horst

doi:10.1002/anie.197606092

Cited by 9 publications

(6 citation statements)

References 15 publications

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“…NMR (270 MHz, C6D6) 2.02 (s, 3 H), 3.94 (tm, J = 5.7 Hz, 2 H), 4.79 (dm, J = 17.0 Hz, 1 H), 4.87 (dm, J = 10.3 Hz, 1 H), 5.34 (ddt, J = 17.1, 10.3, 5.7 Hz, 1 H), 6.67 (d, J = 8.1 Hz, 2 H), 6.83 (d, J = 7.5 Hz, 2 H), 7.27 (br s, 1 H); f'H)13C NMR (50 MHz, CD3CN, 0.07 M Cr(acac)3) 5 21.1 (CH3), 58.3 (NCH2), 118.9 (CH= CH2), 123.3, 129.4 (ortho, meta), 132.9, 138.7, 153.0 (ipso, para, CH=CH2), 199.0 (cis CO, 7i83W_nc = 126 Hz), 204.8 (trans CO, 7i83W_nc = 126 Hz), 255.7 (carbene).…”

Section: Methodsmentioning

confidence: 99%

“…For (£)-4: NMR (270 MHz, C6D6) 1.55 (q, J = 6.4 Hz, 2 H), 2.06 (s, 3 H), 2.47 (q, J = 6.0 Hz, 2 H, NCH2), 4.9 (m, 2 ), 5.18 (m, 1 H), 6.57 (d, J = 6.6 Hz, 2 ), 6.91 (d, J = 7.0 Hz, 2 H), 8.48 (br s, 1 H); 13C NMR (50 MHz, gated decoupled, CD3CN, 0.07 M Cr(acac)3) 21.0 (q, J = 127 Hz, CH3), 49.8 (t, J = 145 Hz, NCH2CH2), 66.0 (t, J = 132 Hz, NCH2), 120.8 (d, J = 162 Hz, ortho or meta), 129.3 (d, J = 159 Hz, ortho or meta), 137.1, 148.4 (s, s, ipso and para), 199.3 (cis CO, yi83W_i3C = 126 Hz), 205.1 (trans CO), 255.9 (carbene), not observed (CH=CH2 and CH=CH2).…”

Section: Methodsmentioning

confidence: 99%

“…Development with 1:2 CH2Cl2-hexane led to the elution of a yellow band consisting of a 1:4.6 mixture of (Z)-3:(£)-3 (36% yield) followed by an orange band. Evaporation of solvent from the orange solution gave 5 as a yellow solid: mp 145-146.5 °C; IR (Nujol) 2020 (s), 1934 (s), 1903 (s), 1840 (s) cm-1; NMR (270 MHz, C6D6) 2.00 (s, 3 ), 2.81 (d, J = 13.2 Hz, 1 H, C=C7/H), 2.94 (br d, J = 14.1 Hz, 1 H, diastereotopic NCH2), 3.06 (d, J = 8.6 Hz, 1 H, C=CH7/), 3.31 (ddd, J = 14.1, 5.1, 1.6 Hz, 1 H, diastereotopic NCH2), 4.09 (ddddd, J = 13.1,8.8,4.8,4.0,0.7 Hz, 1 H, Ctf=CH2), 6.82 (d, J = 8.0 Hz, 2 H), 6.92 (d, J = 8.0 Hz, 2 H), 7.26 (br s, 1 , NH). Decoupling of the secondary vinylic hydrogen by irradiation at 4.09 results in collapse of the terminal vinyl hydrogen resonances at 2.81 and 3.06 to singlets and to simplification of the NCH2 resonance to a doublet at 3.31 (Jlem = 14.3 Hz) and doublet of doublets at 2.94 (Jim = 14.3 Hz, 7NH = 4.1 Hz).…”

Section: Methodsmentioning

confidence: 99%

“…The imine was prepared from allylamine (0.26 g, 4.55 mmol) and p-tolualdehyde (0.5 g, 4.16 mmol) in 10 mL of benzene by azeotropic distillation of water. Vacuum distillation of the reaction mixture gave 6 (0.6 g, 83%): IR (neat) 1650 (s), 1642 (m) cm'1; NMR (270 MHz, C6D6) 2.04 (s, 3 ), 4.08 (dm, J = 5.5 Hz, 2 ), 5.07 (dm, J = 10.5 Hz, 1 H), 5.25 (dm, J = 17.3 Hz, 1 ), 6.06 (ddt, J = 16.4, 10.6, 5.5 Hz, 1 H), 6.96 (d, J = 7.9 Hz, 2 ), 7.70 (d, J = 7.9 Hz, 2 H), 7.97 (s, 1 H). Crystallographic and X-ray Data.…”

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Casey¹,

Shusterman²,

Vollendorf³

et al. 1982

J. Am. Chem. Soc.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Casey¹,

Shusterman²,

Vollendorf³

et al. 1982

J. Am. Chem. Soc.

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“…Here and in Table IV the thermal coefficients have been multiplied by 104. Caled forC14HMF4Fe,04P7S^C. 29.47; , 4.21; P, 10.87; F, 13.33. Found: C, 29.38; H, 4.23; P, 10.52; F, 13.10.1R v(CO): 2017 w, 1977 s, 1953 s cm"1 (CH2C12 solution). NMR: 1.86 (SCH3(s)), 2.20 (SCH3)(d)) yFH = 0.9 Hz, 1.30 ppm PCH3,/PH = 7.8 Hz.…”

Section: Methodsmentioning

confidence: 99%

Insertion of tetrafluoroethylene into the iron-iron bond of (.mu.(SCH3)Fe(CO)3)2, its thermal rearrangement to a bridging carbene ligand, and the transformation of the carbene to a perfluoromethylcarbyne ligand. Structures of .mu.(SCH3)2.mu.(C2F4)Fe2(CO)6 and .mu.(SCH3)2.mu.(FCCF3)Fe2(CO)6 at - 162.degree.C

Bonnet¹,

Mathieu²,

Poilblanc³

et al. 1979

J. Am. Chem. Soc.

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The insertion of tetrafluoroethylene into the Fe-Fe bond of the dinuclear complex (g(SCH3)Fe(CO)3)2 is photochemically induced. When the temperature of the reaction is stabilized at 20 °C, the major product is the yellow dinuclear species ^(SCFÍ3)2^(C2F4)Fe2(C0)6 (1), where C2F4 bridges the Fe atoms with two ff(C-Fe) bonds, the C-C bond being parallel to the Fe-Fe axis. When the temperature is higher, i.e., 35 °C, the product is the red dinuclear species ^(SCH3)2M(FCCF3)Fe2(CO)6 (2), which contains a >CF-CF3 carbene bridge. It is possible by heating 1 to obtain 2 and a mechanism for this reaction is proposed, based in part on a study of the action of BF3 on 1. The action of BF3 on 2, followed by the addition of trimethylphosphine, affords [g(SCH3)2Fe2(CO)3(PCH3)3)2(CCF3)][BF4] (7), which may be a perfluoromethylcarbyne complex. A proof for the two different kinds of insertion of C2F4 is presented in the form of crystal structure determinations of 1 and 2. In 1 each iron atom is octahedrally coordinated to three carbonyl groups, two bridging S atoms, and one C atom of C2F4. The Fe-Fe separation is 3.311 (1) Á, the dihedral angle around theS atoms is 135.0°, and the average Fe-S-Fe angle is 91.6°. Compound 1 crystallizes in the orthorhombic space group D\\-Pbca in a cell of a = 15.029 (8), b = 13.561 (5), c = 15.437 (8) Á. Compound 2 crystallizes with eight formula units in space group C\h-P2\/c of the monoclinic system in a cell of dimensions a = 11.545 (3), b = 16.681 (5), c = 16.830 (6) Á with ß = 97.86 (2)°. Based on 2471 and 4416 unique reflections for 1 and 2, respectively, the structures were refined by full-matrix least-squares techniques to conventional agreement indices (on F) of R = 0.044 and Rw = 0.049 for 1 and R = 0.039 and Rw = 0.048 for 2. In 2, each iron atom is also octahedrally coordinated, being bound as in 1 to three carbonyl groups, two bridging S atoms, but here to the same bridging C atom of the >CF-CF3 carbene group. The Fe-Fe separation averages 2.963 Á, the dihedral angle around the sulfur atoms is 107.2°, and the average Fe-S-Fe angle is 79.39°. The Fe2S2 unit is more compact in 2 than in 1 but less compact than in the starting material (/x(SCH3)Fe(CO)3)2. The flexibility of such molecules around the S-S axis, together with the reactivity of the Fe-Fe bond, is discussed.The study of the reactivity of the metal-metal bond in dinuclear complexes toward alkynes, alkenes, or more generally small unsaturated molecules is an increasing field of interest. This is particularly true for dinuclear complexes with metal to metal multiple bonds.2•3 However, insertion reactions of alkynes and alkenes into metal-metal single bonds in dinuclear

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From Monoolefins

Hartley¹

1991

Inorganic Reactions and Methods

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A CH‐Carbene Complex of Iron by Metal‐Induced Fragmentation of Two Bonds of a Bicyclopentane Unit

Cited by 9 publications

References 15 publications

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

Synthesis and x-ray structure of cis-tetracarbonyl[(Z)-(.eta.2-allylamino)(p-tolyl)carbene]tungsten(0), a stable metal-carbene-alkene complex

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