Dimethylsulfuniumcyclopentadienylidemolybdenum tricarbonyl

Zdanovitch, V.I.; Zhakaeva, A.Zh.; Setkina, V. N.; Kursanov, D. N.

doi:10.1016/s0022-328x(00)87903-6

Cited by 19 publications

(12 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The group 6 tricarbonyl complexes III − V were synthesized using procedures similar to those reported by Kotz et al in the syntheses of the corresponding complexes of I 2b. An excess (2−3 equiv) of M(CO) 6 (M = Cr, Mo) was refluxed in diglyme with II to give the resulting chromium and molybdenum complexes in ∼60% yield for both complexes (Scheme ); however, the tungsten derivative required the use of W(CO) 3 (CH 3 CN) 3 to ensure ligand substitution 2b. An excess of W(CO) 3 (CH 3 CN) 3 was heated with II in diglyme to 110 °C to provide the tungsten complex in 70% yield.…”

Section: Resultsmentioning

confidence: 99%

“…Wilkinson noted soon after the initial Ramirez report that, since Ib would be isoelectronic with benzene, the ylide might be expected to form compounds of the type (η 5 -C 5 H 4 PPh 3 )M(CO) 3 (M = Cr, Mo, W), analogous to the known arene compounds (η 6 -C 6 H 6 )M(CO) 3 . Successful attempts to prepare the group 6 compounds were carried out, and the molybdenum compound was obtained analytically pure,2a although the structures and chemistry of these compounds were only explored many years later. 2b-g Analogous carbonyl complexes of manganese and rhenium, of the type [(η 5 -C 5 H 4 PPh 3 )M(CO) 3 ] + (M = Mn, Re), and a cobalt complex, [(η 5 -C 5 H 4 PPh 3 )Co(CO) 2 ] + , have subsequently been reported, as have a few satisfactorily characterized complexes of I with ruthenium,5a rhodium, 5b,c nickel,5d palladium, 5e-h platinum,5h and mercury. 5i,j However, a number of attempts to prepare complexes of metal halides generally resulted in poorly soluble species of indefinite constitution …”

mentioning

confidence: 99%

“…In part, perhaps, because of difficulties in characterizing many of the compounds obtained, research in this area stagnated and virtually no publications dealing with the coordination chemistry of I have appeared in over two decades. − However, the donor properties of I and similar ligands are expected to fall between those of benzene and the cyclopentadienyl (Cp) ligand and, given the enormous importance of Cp and related complexes, this lack of interest seems quite surprising. Furthermore, while complexes of I have been found to contain the ligand bound to the metal in an η 5 fashion, coordination in an η 1 fashion has been demonstrated 5i and coordination could in principle also occur in the η 2 , η 3 , and η 4 modes.…”

mentioning

confidence: 99%

See 2 more Smart Citations

New Complexes of Methyldiphenylphosphonium Cyclopentadienylide, Representative of a Class of Ligands Heretofore Much Neglected

2007

View full text Add to dashboard Cite

Methyldiphenylphosphonium cyclopentadienylide, C5H4PMePh2 (II), has been synthesized and characterized spectroscopically and crystallographically and has been found to exhibit properties consistent with the zwitterionic structure IIb. The new group 6 coordination complexes (η5-C5H4PMePh2)M(CO)3 have been synthesized via substitution reactions of II with M(CO)6 (M = Cr, Mo) or W(CO)3(MeCN)3. Comparisons of ν(CO) values of these complexes with those of the isoelectronic (η6-C6H6)M(CO)3 and [(η5-C5H5)M(CO)3]- suggest that the electron-donating ability of the ylide is less than that of the cyclopentadienyl anion but much greater than that of benzene. Thermal and photochemical substitutions of the CO ligands of (η5-C5H4PMePh2)M(CO)3 (M = Cr, Mo) by equimolar amounts of PMe3 and PPh3 were not observed, but the ylide is displaced photochemically from (η5-C5H4PMePh2)Mo(CO)3 by excess PMe3 to form fac-Mo(CO)3(PMe3)3, while (η5-C5H4PMePh2)Mo(CO)3 reacts with I2 to form [(η5-C5H4PMePh2)Mo(CO)3I]I. The crystal structures of the free ylide and all four of its coordination complexes show that in each case one of the ylide phenyl rings not only eclipses the C5H4 ring but also is oriented toward it in an edge-on fashion. The intramolecular edge−face orientations involve interactions of an aromatic hydrogen atom with the C5H4 aromatic π systems and are rationalized in terms of electrostatic attractive forces between the slightly positive phenyl hydrogen atom and the negatively charged C5H4 ring. The electronic structures of II and of (η5-C5H4PMePh2)Cr(CO)3 have been investigated using ab initio methodologies; it is found that the near-degenerate HOMO and HOMO-1 orbitals of the free ylide exhibit symmetries very similar to those of the corresponding, doubly degenerate HOMO of the cyclopentadienyl anion (E1 symmetry) and that a lower energy, almost fully symmetric orbital corresponds to the fully symmetric bonding A1 MO of the cyclopentadienyl anion. In none of these three orbitals does there appear to be significant π involvement of an orbital on the phosphorus atom, consistent with the low P−C bond order implicit in the zwitterionic structure IIb. The primary ylide−metal interactions in (η5-C5H4PMePh2)Cr(CO)3 involve donation of the HOMO and HOMO-1 orbitals into the d xz and d yz orbitals of the chromium, while the calculated ylide−Cr(CO)3 bond dissociation energy is about 30% higher than the analogous ring−metal bond dissociation energy of (η6-C6H6)Cr(CO)3.

show abstract

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

New Complexes of Methyldiphenylphosphonium Cyclopentadienylide, Representative of a Class of Ligands Heretofore Much Neglected

2007

View full text Add to dashboard Cite

show abstract

“…•7c-Rh" 3.9) (Jcp-92.5) (JCp-9.8) (Jcp-118) (/cp " 2) (/c-Rh-9.8) (/CP = 9.8, •7c-Rh = [5][6][7][8][9] (/cp-11-8,…”

Section: Resultsmentioning

confidence: 99%

.eta.5-(Triphenylphosphonium cyclopentadienylide-rhodium(I) and -rhodium(III) complexes

Tresoldí¹,

Recca²,

Finocchiaro³

et al. 1981

Inorg. Chem.

View full text Add to dashboard Cite

“…After the discovery of ferrocene in 1951, , metal complexes of various Cp ylides were also reported. ,− The group 6 tricarbonyl Cp complexes of fulvenes, pyridinium cyclopentadienylides, phosphonium cyclopentadienylides, − and sulfonium cyclopentadienylides , as well as of arenes and cyclopentadienide , are generally prepared from the hexacarbonyl or tris(acetonitrile) tricarbonyl precursor and the respective ligand in refluxing alkanes or ethers. We reported on the first imidazolium Cp carbonyl complex, which was synthesized from ylide B and tungsten hexacarbonyl in tetrahydrofuran under irradiation with UV light …”

Section: Introductionmentioning

confidence: 99%

Group 6 Carbonyl Complexes of C-Ylidic Cp Ligands

2020

View full text Add to dashboard Cite

The synthesis and the analytical features of group 6 carbonyl complexes of electron-poor mono(imidazolium)-and bis(imidazolium)-substituted Cp ylides are presented. With the neutral ylidic imidazolium Cp and the monocationic 1,3bis(imidazolium) Cp ligand all of the group 6 carbonyl complexes were prepared, while in the case of the 1,2-disubstituted Cp ylide only the chromium Cp complex was accessible. The donor properties of the ligands were elucidated experimentally by means of the CO stretching frequencies of their group 6 metal complexes and theoretically by DFT calculations. Every imidazolium substituent and the planar conjugated π system of the imidazolium moieties annelated to the Cp ring increase the average CO stretching frequencies by about 20 cm −1 . Overall, the donor properties of the C-ylidic Cp ligands are still stronger than those of the benzene ligand. Additionally, the protonation of the Cp ligands was investigated, and the basicity correlates qualitatively with the electron-donor character of the ylidic Cp ligands.

show abstract

Dimethylsulfuniumcyclopentadienylidemolybdenum tricarbonyl

Cited by 19 publications

References 4 publications

New Complexes of Methyldiphenylphosphonium Cyclopentadienylide, Representative of a Class of Ligands Heretofore Much Neglected

New Complexes of Methyldiphenylphosphonium Cyclopentadienylide, Representative of a Class of Ligands Heretofore Much Neglected

.eta.5-(Triphenylphosphonium cyclopentadienylide-rhodium(I) and -rhodium(III) complexes

Group 6 Carbonyl Complexes of C-Ylidic Cp Ligands

Contact Info

Product

Resources

About