Trigonal-Prismatic versus Octahedral Molecular Structures in [(CH3)nMX6−n] Compounds

Roessler, Beatrice; Pfennig, Valérie; Seppelt, Konrad

doi:10.1002/1521-3765(20010903)7:17<3652::aid-chem3652>3.3.co;2-a

Cited by 3 publications

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“…Experimental data are still scarce on these types of molecules. (CH 3 ) 5 MoOCH 3 and (CH 3 ) 5 W−Cl are clearly distorted trigonal prismatic . The OCH 3 and Cl ligands occupy a position in the hemisphere where the short M−C and opened C−M−C methyl groups reside in Mo(CH 3 ) 6 and W(CH 3 ) 6 , respectively.…”

Section: D0 and D1 Transition Metal Complexesmentioning

confidence: 98%

“…The OCH 3 and Cl ligands occupy a position in the hemisphere where the short M−C and opened C−M−C methyl groups reside in Mo(CH 3 ) 6 and W(CH 3 ) 6 , respectively. The only known example with two X ligands, (CH 3 ) 4 Mo(OCH 3 ) 2 , has a similar structure . (CH 3 ) 3 WCl(OCH 3 ) 2 is an accidental oxidation product of (CH 3 ) 5 WCl, it is the only compound currently known with x = 3, and it has a structure based on an octahedron .…”

Section: D0 and D1 Transition Metal Complexesmentioning

confidence: 99%

“…(CH 3 ) 5 MoOCH 3 and (CH 3 ) 5 W-Cl are clearly distorted trigonal prismatic. 47 The OCH 3 and Cl ligands occupy a position in the hemisphere where the short M-C and opened C-M-C methyl groups reside in Mo(CH 3 ) 6 and W(CH 3 ) 6 , respectively. The only known example with two X ligands, (CH 3 ) 4 Mo(OCH 3 ) 2 , has a similar structure.…”

Section: Transition Metal Complexesmentioning

confidence: 99%

“…The only known example with two X ligands, (CH 3 ) 4 Mo(OCH 3 ) 2 , has a similar structure. 47 (CH 3 ) 3 WCl(OCH 3 ) 2 is an accidental oxidation product of (CH 3 ) 5 WCl, it is the only compound currently known with x ) 3, and it has a structure based on an octahedron. 47 Somewhere at this stage of substitution, the transition from trigonal prismatic to octahedral occurs, and a complicated isomer problem and dynamic behavior can be anticipated for these yet largely unknown compounds.…”

Section: Transition Metal Complexesmentioning

confidence: 99%

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Nonoctahedral Structures

Seppelt

2003

Acc. Chem. Res.

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There is always a special reason when six-coordinate molecules or complexes are nonoctahedral. The Jahn-Teller distortion is the longest known example. Also well understood now is the steric activity or nonactivity of a nonbonding electron pair, for example XeF(6). In the past few years, it became obvious that six-coordinate d(0) and d(1) complexes with sigma only ligands such as Mo(CH3)(6) are far from octahedral; rather, they are trigonal prismatic or even C(3v) distorted trigonal prismatic. This phenomenon can be explained with simple molecular orbital or valence bond models.

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Section: D0 and D1 Transition Metal Complexesmentioning

confidence: 98%

Section: D0 and D1 Transition Metal Complexesmentioning

confidence: 99%

Section: Transition Metal Complexesmentioning

confidence: 99%

Section: Transition Metal Complexesmentioning

confidence: 99%

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Nonoctahedral Structures

Seppelt

2003

Acc. Chem. Res.

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“…Experimentally, not much is known about mixed‐substituted compounds: [W(CH 3 ) 5 Cl], [Mo(CH 3 ) 5 OCH 3 ], and [Mo(CH 3 ) 4 (OCH 3 ) 2 ] are all trigonal prismatic, whereas [W(CH 3 ) 3 Cl(OCH 3 ) 2 ] is octahedral 12. Another compound of interest here, [W(CH 3 )Cl 5 ], has been prepared several times, but has not yet been characterized structurally 13.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Investigation of the Nonrigid Six‐Coordinate Compounds [Mo(R)F₅], [W(R)F₅], and Related Compounds

Quiñones

Seppelt

2006

Chemistry A European J

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Density functional calculations for [M(CH3)F5], [M(CF3)F5], [M(CH3S)F5], and [M(CF3S)F5] (M=Mo, W) show that they are expected to be nonrigid molecules, with energy barriers for the octahedral-trigonal-prismatic interchange as low as 7.2 kJ mol(-1). The ground state for the CH3- and CF3- compounds is trigonal prismatic, for the CH3S- and CF3S- compounds, (distorted) octahedral. All calculated compounds [M(C6F5)nF(6-n)] (M=Mo, W) have a trigonal-prismatic ground state, whereas the situation for [M(C6H5)nF(6-n)] (M=Mo, W) is more complex.

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Syntheses and Structures of Cationic and Neutral, Homo- and Heteroleptictert-Butoxides of the Group 4 Metals

2010

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The utility of tri-tert-butoxystannate as a chelating tridentate ligand for group 4 metals was investigated. The highly Lewis acidic metals degraded the stannate ion in a series of tert-butoxide abstraction steps to produce a variety of group 4 tert-butoxides. A total of 1 equiv of NaSn(O(t)Bu)(3) reacted with cis-MCl(4)(THF)(2) [M = Zr (1), Hf (2)] in THF solutions to furnish the salts fac-{[M(O(t)Bu)(3)(THF)(3)](SnCl(3))}, which are separated ion pairs featuring weakly coordinating trichlorostannate ions. Neutral complexes, namely, [M(O(t)Bu)(2)Cl(2)(THF)(2)] [M = Zr (3), Hf (4)], were isolated when 2/3 equiv of sodium stannate was used in these reactions. Titanium tetrachloride formed analogues neither of 1 and 2 nor of 3 and 4, but Ti(O(t)Bu)(3)Cl reacted with silver triflate to give [Ti(O(t)Bu)(2)(OTf)(2)(THF)(2)] (5). Anion exchange of triflate for trichlorostannate transformed 1 to the contact ion pair fac-[Zr(O(t)Bu)(3)OTf(THF)(2)] (6). A total of 2 equiv of NaSn(O(t)Bu)(3) reacted with cis-MCl(4)(THF)(2) to give the complexes fac-[Sn(mu-O(t)Bu)(3)M(O(t)Bu)(3)] [M = Zr (7), Hf (8)]. Tri-tert-butoxystannate may be used as a selective alkoxylating agent for group 4 metals, and it can be transferred to these metals intact if their Lewis acidity is appropriately attenuated as in fac-{[M(O(t)Bu)(3)(THF)(3)](SnCl(3))}. Single-crystal X-ray studies revealed distorted octahedral coordination geometries for all compounds (1-8), with 1, 2, 7, and 8 being crystallographically C(3) symmetric.

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Trigonal-Prismatic versus Octahedral Molecular Structures in [(CH3)nMX6−n] Compounds

Cited by 3 publications

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Nonoctahedral Structures

Nonoctahedral Structures

A Theoretical Investigation of the Nonrigid Six‐Coordinate Compounds [Mo(R)F₅], [W(R)F₅], and Related Compounds

Syntheses and Structures of Cationic and Neutral, Homo- and Heteroleptictert-Butoxides of the Group 4 Metals

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Trigonal-Prismatic versus Octahedral Molecular Structures in [(CH3)nMX6−n] Compounds

Cited by 3 publications

References 0 publications

Nonoctahedral Structures

Nonoctahedral Structures

A Theoretical Investigation of the Nonrigid Six‐Coordinate Compounds [Mo(R)F5], [W(R)F5], and Related Compounds

Syntheses and Structures of Cationic and Neutral, Homo- and Heteroleptictert-Butoxides of the Group 4 Metals

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Product

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A Theoretical Investigation of the Nonrigid Six‐Coordinate Compounds [Mo(R)F₅], [W(R)F₅], and Related Compounds