Dibenzophosphasemibullvalen

Geier, Jens; Frison, Gilles

doi:10.1002/ange.200351388

Cited by 6 publications

(3 citation statements)

References 26 publications

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“…None of the species in Table 1 is likely be isolated, because insertion of a coordinated C 2 H 4 into the RhH or RhSi bond is expected (Rh I complexes are efficient catalysts for hydrogenation and hydrosilylation). Therefore we synthesized bis(5 H ‐dibenzo[ a , d ]cyclohepten‐5‐yl)methylsilane (trop 2 SiHMe, 2 ), in which this insertion is unlikely to occur because of resulting strain energy in the product 11. Silane 2 is easily obtained in 85 % overall yield from 5‐chloro‐5 H ‐dibenzo[ a , d ]cycloheptene (tropCl, 1 ), which was first metalated with elemental lithium and then coupled in situ with MeHSiCl 2 (Scheme ).…”

Section: Methodsmentioning

confidence: 99%

Trigonal Pyramids: Alternative Ground‐State Structures for Sixteen‐Electron Complexes

Ostendorf

Landis

2006

Angewandte Chemie

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[1] However, apart from tetrahedral structure T, which is observed for high-spin transition metals from the 4th period, [2] sawhorse (SH, C 2v ) and trigonalpyramidal structures (TP, C 3v ) are alternatives (Scheme 1).[3]The highly reactive transient carbonyls [M(CO) 4 ] (M = Fe, Ru, Os) have SH structures, [4a-c] as do a few recently isolated Ru 0 and Rh I complexes, which show remarkable reactivity.Even computationally, the TP structure has been rarely considered. Pidun and Frenking investigated by DFT methods [RhX(CO) 3 ] complexes with X = H, HC = O, CH 2 OH, and OMe. For [Rh(HC = O)(CO) 3 ], TP is the (slightly) preferred ground-state structure, whereas all other complexes have either a P or an SH form in the global minimum.[5] Within the complementary spherical electron density (CSED) model, Mingos identified SH and TP forms as the next best choices to planar structures for 16-electron complexes of late transition metals. [6] In computations using the orbital ranked symmetry analysis method (ORSAM), Bayse and Hall considered d 8 -MH 4 hydrides with SH and TP forms.[7] Proposals for making Scheme 1. Planar (P), tetrahedral (T), sawhorse (SH), and trigonalplanar (TP) structures.

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Section: Methodsmentioning

confidence: 99%

Trigonal Pyramids: Alternative Ground‐State Structures for Sixteen‐Electron Complexes

Ostendorf

Landis

2006

Angewandte Chemie

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“…The dibenzo[ a , d ]cycloheptatrienyl (trop) platform was used for the synthesis of the highly strained dibenzophosphasemibullvalene D ,8 very robust aminophosphiranes (BABAR‐Phos) E ,9 and the phosphiranium ion F (R= i Pr, R 1 = t Bu; Scheme ) 10. Isolated examples of the latter are likewise rare 11…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Structure, and Reactivity of a Stabilized Phosphiranylium Salt

Jansen¹,

Läng²,

Slootweg³

et al. 2010

Angewandte Chemie

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“…Species such as A (phosphirenylium ion) or B (phosphiranylium ion), which may be viewed as p-complexes of P + to alkynes or alkenes, [5] respectively (Scheme 1), have never been isolated. [6] A notable exception is the crystalline diphosphirenium ion C. [7] The dibenzo[a,d]cycloheptatrienyl (trop) platform was used for the synthesis of the highly strained dibenzophosphasemibullvalene D, [8] very robust aminophosphiranes (BABAR-Phos) E, [9] and the phosphiranium ion F (R = iPr, R 1 = tBu; Scheme 1). [10] Isolated examples of the latter are likewise rare.…”

Section: In Memory Of Pascal Le Flochmentioning

confidence: 99%