1996
DOI: 10.1021/om960331d
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Four-Legged Piano Stool Molybdenum(II) Compounds without Carbonyl Ligands. 4. Cyclopentadienylmolybdenum(II) Complexes with 16-Electron and 18-Electron Configurations

Abstract: Monocyclopentadienyl complexes of Mo(II) with 16-and 18-electron configurations of the form (Ring)MoClL x (x ) 2, Ring ) Cp, L ) PMe 2 Ph; x ) 2, Ring ) Cp*, L ) PMe 3 , PMe 2 Ph, L 2 ) dppe; x ) 3, Ring ) Cp, L ) PMe 2 Ph) are described. All of the 16-electron complexes are paramagnetic with an S ) 1 ground state, as shown by magnetic measurements in the solid state and in solution, and by the contact-shifted 1 H NMR spectra. The structure of Cp*MoCl(dppe) was determined by X-ray diffraction methods. The 18-e… Show more

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Cited by 41 publications
(66 citation statements)
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“…The crystal data show that the phenyl moiety is orientated to the sterically more demanding side of the complex. The Mo1–P1 bond length [246.82(7) pm] is in good accordance with those of the previously reported molybdenum phosphane adducts [245.3(2)–248.6(2) pm] 15b,16. The Si1–S1–Si1′ angle [105.30(4)°] is in the expected range for a two‐coordinate sulfur atom.…”
Section: Resultssupporting
confidence: 89%
“…The crystal data show that the phenyl moiety is orientated to the sterically more demanding side of the complex. The Mo1–P1 bond length [246.82(7) pm] is in good accordance with those of the previously reported molybdenum phosphane adducts [245.3(2)–248.6(2) pm] 15b,16. The Si1–S1–Si1′ angle [105.30(4)°] is in the expected range for a two‐coordinate sulfur atom.…”
Section: Resultssupporting
confidence: 89%
“…[35] Interestingly, if the H2 and H3 atoms are considered as defining a stretched H 2 ligand, therefore occupying a single coordination position in a Mo II complex, then the coordination geometry would be described as a "four-legged piano stool", which is indeed a quite common geometrical arrangement for Mo II , [36] as exemplified by [MoCpA C H T U N G T R E N N U N G (PMe 2 Ph) 3 Cl] [37] and [MoCp-A C H T U N G T R E N N U N G (dppe)(CO)H]. [38] The NMR properties of 2 a and 2 b confirm the presence of three hydride ligands.…”
Section: Wwwchemeurjorgmentioning
confidence: 99%
“…Calculations of RÀX coordination, atom transfer, and halide exchange with model compounds: On the basis of the results presented above and our previously formulated hypothesis, [14] the initiator molecule should be able to coordinate to the 15- 2 ] was also shown to catalyze the polymerization of styrene by ATRP, [19] and by the fact that the product of atom transfer, the 18-electron organometallic Mo IV species [Mo(Cp)Cl 3 (PMe 3 ) 2 ] is also a well-characterized compound, [20] whereas analogues containing dadtype ligands have not been reported so far. All optimized compounds were obtained from starting geometries adapted from crystallographically characterized analogues: [RuCl 2 -(PPh 3 ) 3 ], [21] [MoCl 3 (PMe 2 Ph) 3 ], [22] [MoCl 4 (PMe 2 Ph) 3 ], [23] [Mo(Cp)Cl 2 (PMe 3 ) 2 ], [24] and [Mo(Cp)Cl 3 (PMe 2 Ph) 2 ].…”
Section: Resultsmentioning
confidence: 94%