Reactivity of [CpCr(CO)3]2 towards thione (CS) moieties in some sulfur-containing substrates

Ng, Victor Wee Lin; Kuan, Seah Ling; Weng, Zhiqiang; Leong, Weng Kee; Vittal, Jagadese J.; Koh, Lip Lin; Tan, Geok Kheng; Goh, Lai Yoong

doi:10.1016/j.jorganchem.2005.03.001

Cited by 8 publications

(4 citation statements)

References 44 publications

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“…There thus exists a strained three-membered CrS 2 ring, with a small S−Cr−S bond angle [53.57(3)° in 3a , 54.29(2)° in 3c ]. These angles are larger than those in Cp 2 Cr 2 (CO) 4 (μ−η 2 -S 2 ) [48.8(0)° and 49.0(0)°] and in Cp 2 Cr 2 (CO) 5 (μ−η 1 ,η 2 -S 2 ) [50.1(1)°], which undoubtedly are related to the shorter S−S bonds of 1.990(1) and 2.010(4) Å, respectively,38c but they are, as expected, smaller than the “open” S−Cr−S angles (70.3°−83.65°) found in CpCr(CO) 2 complexes containing bidentate S 2 PPh 2 , S 2 P(O i Pr) 2 , S 2 CNR 2 ,5b and S 2 CO i Pr ligands . The Cr−S bond lengths [range 2.3334(12)−2.3688(7) Å] lie at the low end of the range previously observed for other CpCr complexes, viz.…”

Section: Resultssupporting

confidence: 55%

Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Lau

Ang

et al. 2007

Inorg. Chem.

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The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.

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Section: Resultssupporting

confidence: 55%

Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Lau

Ang

et al. 2007

Inorg. Chem.

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“…The chromium(III) complex 11 was stable in air and NMR-silent and was characterized by its IR spectrum and X-ray crystal structure analysis (Figure ). Related cyclopentadienyl chromium dithiocarbonate complexes such as Cr(η 5 -C 5 H 5 )(η 2 -S 2 CO i Pr)(CO) 2 have been crystallographically characterized . Because metal−dithiocarbonates are related to metal−carbonates, activation of carbon dioxide using a precursor of the dithiocarbonates may be an interesting subject of future studies .…”

Section: Resultsmentioning

confidence: 99%

Group 6 Metal Complexes of the η⁵-Pentamethyl[60]fullerene

Iwashita

Nakamura

2008

Organometallics

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A molybdenum pentamethyl[60]fullerene bromo tricarbonyl complex, Mo(η 5 -C 60 Me 5 )Br(CO) 3 (3), was successfully synthesized by the reaction of C 60 Me 5 Br (2) with Mo(CO) 3 (EtCN) 3 . Treatment of 3 with I 2 afforded an iodo complex, Mo(η 5 -C 60 Me 5 )I(CO) 3 (4). The reaction employing C 60 Me 5 K (5) prepared from C 60 Me 5 H (1) and KH, followed by treatment with Mo(CO) 3 (EtCN) 3 and then Diazald, gave a nitrosyl complex, Mo(η 5 -C 60 Me 5 )(NO)(CO) 2 (6). Complex 6 was converted to a molybdenum(IV) complex, Mo(η 5 -C 60 Me 5 )Cl 2 (NO)(CO) (7), by the reaction with PCl 5 . A molybdenum(VI) complex, Mo(η 5 -C 60 Me 5 )O 2 Br (8), was obtained by exposure of 3 in air. Tungsten-and chromium-nitrosyl complexes, W(η 5 -C 60 Me 5 )(NO)(CO) 2 (9) and Cr(η 5 -C 60 Me 5 )(NO)(CO) 2 (10), were synthesized similarly to 6. Complex 10 gave a dithiocarbonate complex, Cr(η 5 -C 60 Me 5 )(η 5 -S 2 COEt)(NO) (11) through the reaction among 10, ethanol, and carbon disulfide. Compounds 1, 3, 4, 6, 8, and 11 were characterized by X-ray crystallography.

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“…To our knowledge, there is only one other structure in the literature with a comparable geometry, namely VIII (the entry with refcode RATROU in Table 5), in which a CpCr fragment is bound in a side-on manner through the C and S atom of the organic fragment, forming a three-membered Cr-S-C chelate ring; in this structure, wherein the Cr-S bond length is comparable to that found in 2 -DTDAs, the Cr-C distance is also rather long at 2.144(3) Å, a value that is well within the single-bond range. 44 The ligand bite angle (N-Cr-S) is very similar in both molecules (44.89(11)°in 6a and 44.65(9)°in 6b). The Cr-N-S and Cr-S-N angles are also similar (73.80 (14)°and 61.31 (13)°in 6a, 73.94(12)°and 61.41 (11)°in 6b, respectively).…”

Section: Bond Ordermentioning

confidence: 88%

“…The value of a Cr-S single bond length is established in three different ways: First, the sums of the covalent radii as recently redetermined by Cordero et al 71 gives a value of 2.440 Å. Second, the structure types for which a single bond is expected based on chemical intuition, specifically terminal thiolato derivatives of CpCr(CO) 3 (structures with refcodes MAKLOA, RATRIO, and XULGOY), have Cr-S bond distances of 2.4485(8), 44 2.448(3), 47 and 2.4406(8) Å, 49 respectively. Lastly, the full distribution between 2.37 and 2.52 Å for structure types that provide the major Gaussian distribution in the histogram (Fig.…”

Section: Bond Ordermentioning

confidence: 99%

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

et al. 2015

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Coordination complexes of thiazyl rings -Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO) x (x = 2, 3) complexes of fluorinated and nonfluorinated 1 3 -1,2,4,6-thiatriazinyls with differing Cr-S bond orders Abstract: The reaction of [3,5-Ph 2 -C 2 N 3 S] 2 with [CpCr(CO) 3 ] 2 in toluene at room temperature forms an adduct via a Cr-S bond, formulated as CpCr(CO) 3 SN 3 C 2 Ph 2 , which has fitting NMR, IR, and combustion analysis data. The structure was determined by a single-crystal X-ray structure diffraction study (P2 1 /n, a = 8.4611(17) Å, b = 20.509(4) Å, c = 11.757(2) Å, ␤ = 104.453(7)°). The Cr-S bond length of 2.4908(11) Å corresponds to a bond order of 1.0 from >90 values for CpCr(CO) x or Cp*Cr(CO) x moieties (x = 2, 3) bonded to S, which are used to establish a Pauling-type bond order scale specific to this class of compounds. Similar reactions of fluorinated thiatriazinyls derived from [3-Ph-5-CF 3 -C 2 N 3 S] 2 or [4-MeOC 6 H 4 -5-CF 3 -C 2 N 3 S] 2 are accompanied by the loss of CO to produce CpCr(CO) 2 SN 3 C 2 PhCF 3 (P1, a = 8.0929(8) Å, b = 10.3160(10) Å, c = 11.2405(11) Å, ␣ = 70.032(2)°, ␤ = 72.076(2)°, ␥ = 82.375(2)°) and CpCr(CO) 2 SN 3 (CCF 3 )(C 6 H 4 OCH 3 ) (P2 1 /c, a = 8.1311(7) Å, b = 24.284(2) Å, c = 9.1025(8) Å, ␤ = 97.218(2)°), also fully characterized by spectroscopy and crystallography. Their measured Cr-S bond lengths, 2.2987(14) and 2.2965(11) Å, correspond to bond orders of 1.5. (U/R)B3PW91/6-311+G(2df,2p)//B3PW91/6-31G(2d,p) hybrid density functional theory (DFT) calculations show that the tricarbonyl complex has an unusual bond. However, the dicarbonyl complexes of the fluorinated thiatriazinyls are bonded.

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Reactivity of [CpCr(CO)3]2 towards thione (CS) moieties in some sulfur-containing substrates

Cited by 8 publications

References 44 publications

Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Group 6 Metal Complexes of the η⁵-Pentamethyl[60]fullerene

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

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Reactivity of [CpCr(CO)3]2 towards thione (CS) moieties in some sulfur-containing substrates

Cited by 8 publications

References 44 publications

Coupling of CpCr(CO)3and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Coupling of CpCr(CO)3and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Group 6 Metal Complexes of the η5-Pentamethyl[60]fullerene

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ3-1,2,4,6-thiatriazinyls with differing Cr–S bond orders

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Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Coupling of CpCr(CO)₃and Heterocyclic Dithiadiazolyl Radicals. Synthetic, X-ray Diffraction, Dynamic NMR, EPR, CV, and DFT Studies

Group 6 Metal Complexes of the η⁵-Pentamethyl[60]fullerene

Coordination complexes of thiazyl rings — Synthesis, structure, and density functional theory (DFT) computational analysis of CpCr(CO)_x(x= 2, 3) complexes of fluorinated and nonfluorinated 1λ³-1,2,4,6-thiatriazinyls with differing Cr–S bond orders