Crystal and molecular structures of decamethylmanganocene and decamethylferrocene. Static Jahn-Teller distortion in a metallocene

Freyberg, Derek P.; Robbins, John L.; Raymond, Kenneth N.; Smart, James C.

doi:10.1021/ja00498a017

Cited by 229 publications

(168 citation statements)

References 3 publications

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“…The only other manganocene whose electronic structure has been studied extensively is (Me 5 C 5 ) 2 Mn. [15][16][17] The magnetic moment in the solid state (5-100 K) shows it to be lowspin and its EPR spectrum in frozen glasses and solid solutions of (Me 5 C 5 ) 2 Fe show that the ground state is 2 E 2g , consistent with the gas phase PES data. The room temperature solid-state X-ray crystal structure of (Me 5 C 5 ) 2 Mn with the Mn-C(ave) distances of 2.11 Å show it is low-spin but there are several distortions, which have been ascribed to a static Jahn-Teller distortion.…”

Section: Introductionsupporting

confidence: 76%

“…The room temperature solid-state X-ray crystal structure of (Me 5 C 5 ) 2 Mn with the Mn-C(ave) distances of 2.11 Å show it is low-spin but there are several distortions, which have been ascribed to a static Jahn-Teller distortion. 16 Herein, we report the synthesis, molecular structure and electronic properties of a series of trimethylsilyl and tert-butyl substituted manganocenes.…”

Section: Introductionmentioning

confidence: 99%

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Supramolecular Catalysis of Orthoformate Hydrolysis in Basic Solution: An Enzyme-Like Mechanism

2008

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Abstract. Magnetic susceptibility measurements and X-ray data confirm that tert-butyl substituted manganocenes [(Me 3 C) n C 5 H 5-n ] 2 Mn (n= 1, 2) follow the trend previously observed with the methylated manganocenes, i.e., electron donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp 2 Mn and exhibit higher spin-crossover (SCO) temperatures.However, introducing three CMe 3 groups on each ring gives a temperature invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Mn is due to the significant bulk of the [1,2,4-(Me 3 C) 3 C 5 H 2 ] -ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me 3 C) 2 C 5 H 3 ] 2 Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis (∆T c = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe 3 substituted 2 manganocenes [(Me 3 Si) n C 5 H 5-n ] 2 Mn (n= 1, 2, 3) show high-spin configuration in these cases. Although tetra-and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarily to [(Me 3 C)(Me 3 Si)C 5 H 3 ] 2 Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me 3 C)(Me 3 Si)C 5 H 3 ] 2 Mn on rapid cooling.

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Section: Introductionsupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Supramolecular Catalysis of Orthoformate Hydrolysis in Basic Solution: An Enzyme-Like Mechanism

2008

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“…(d) Parameters adjusted for the effects of thermal motion are given in parentheses. * References (ED: electron diffraction): (1) Gard, Haaland, Novak & Seip (1975); (2) Almenningen, Haaland & Motzfeldt (1967); (3) Freyberg, Robbins, Raymond & Smart (1979); (4) Haaland & Nilsson (1968); (5) Seiler & Dunitz (1979a,b); (6) Almenningen, Gard & Haaland (1976); (7) Bfinder & Weiss (1975); (8) Hedberg & Hedberg (1970); (9) Seller & Dunitz (1980); (10) Tuggle & Weaver (1971); (11) Siebert, Bochmann, Edwin, Kriiger & Tsay (1978); (12) this paper; (13) Beer et al (1973); (14) Pipal & Grimes (1978); (15) Siebert, Renk, Kinberger, Bochmann & Krfiger (1976); (16) Siebert, B6hle & Kriiger (1980 (Fig. 4) with an approximate transition enthalpy of 0.12 kJ mo1-1 was detected.…”

Section: Comparison Of the Two Structuresmentioning

confidence: 99%

The structure of μ-(η-cyclopentadienyl)-bis[(η-cyclopentadienyl)nickel(III)] tetrafluoroborate at 190 and 295 K

Dubler¹,

Textor²,

Oswald³

et al. 1983

Acta Crystallogr Sect B

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“…This is shown, by way of example, by the observation that dicyclopentadienylmanganese 11 has a polymeric constitution in the solid state 12 whereas bis(pentamethylcyclopentadienyl)manganese is monomeric. 13 In this paper we describe some coordination complexes of A blue colored solution developed immediately which slowly turned brown~red at room temperature. The suspension was ref1uxed for 12 h.…”

mentioning

confidence: 99%

“…6798 ( 7) .7042 (3) .0842 ( 7) C (2) .6761 (7) ,7487(3) '1800(7) C (3) .5646 (6) .7425 (3) 0 2186 ( 7) C (4) .4987 ( 7) .6941 (3) .1460(8) C (5) .5690 (7) .6696 (3) .0648(7) C (6) .7800 (9) .6958 (4) .0100(9) C (7) '7678 (9) .7977 (4) .230(1) C (8) .5228 (9) .7833 (4) .3187(9) C (9) .3702 (8) .6773 (4) .145(1) C (10) 0 5317 ( 9) .6187 (4) ~-.0330 (9) c ( 11) '5689 (7) '5485 ( 3) .3764 (7) c ( 12) .5574 (6) .5975 (3) .4573 (8) c ( 13) .6705 (8) .6105 (4) .5355 (7) c ( 14) '7541 ( 7) .5678(4) 0 5021 ( 7) C (15) . 6907 ( 7) .5303 (3) .4034 (8) c ( 16) .4690 (9) .5162 …”

mentioning

confidence: 99%

Divalent lanthanide chemistry. Bis (pentamethylcyclopentadienyl) europium(II) and -ytterbium(II) derivatives: crystal structure of bis (pentamethylcyclopentadienyl) (tetrahydrofuran ytterbium(II) -hemitoluene at 176 K

Tilley¹,

Andersen²,

Spencer³

et al. 1980

Inorg. Chem.

173

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Crystal and molecular structures of decamethylmanganocene and decamethylferrocene. Static Jahn-Teller distortion in a metallocene

Cited by 229 publications

References 3 publications

Supramolecular Catalysis of Orthoformate Hydrolysis in Basic Solution: An Enzyme-Like Mechanism

Supramolecular Catalysis of Orthoformate Hydrolysis in Basic Solution: An Enzyme-Like Mechanism

The structure of μ-(η-cyclopentadienyl)-bis[(η-cyclopentadienyl)nickel(III)] tetrafluoroborate at 190 and 295 K

Divalent lanthanide chemistry. Bis (pentamethylcyclopentadienyl) europium(II) and -ytterbium(II) derivatives: crystal structure of bis (pentamethylcyclopentadienyl) (tetrahydrofuran ytterbium(II) -hemitoluene at 176 K

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