Synthesis, Spectroscopic Properties, and Reactivity of Ferrocenyl(2,4,6-tri-<i>tert</i>-butylphenyl)diphosphene

Pietschnig, Rudolf; Niecke, Edgar

doi:10.1021/om950384f

Cited by 49 publications

(38 citation statements)

References 16 publications

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“…The phosphorus-phosphorus bond lengths of (Z,Z)-1b Á W(CO) 4 (2.038(6) and 2.046(5) Å ) are substantially shorter than the typical P-P single-bond length (ca. 2.19-2.24 Å ), 14 whereas they are within the range of the reported P=P double-bond lengths (1.985-2.049 Å ) for (E)-diphosphenes, 1a,4f,4h,4l and very close to that (2.039 (3) Moreover, the six P-W-C and four C-W-C angles are in the range from 88.3(5) to 93.5(4) and from 87.9(7) to 93.3 (6) , respectively, where the tungsten center of (Z,Z)-1b Á W(CO) 4…”

Section: Complexsupporting

confidence: 52%

“…1,1 0 -Bis[bis(diethylamino)phosphino]ferrocene (5) was quantitatively synthesized by the reaction of bis(diethylamino)chlorophosphine with 1,1 0 -dilithioferrocene prepared from 1,1 0 -dibromoferrocene. The reaction of 5 with hydrogen chloride in ether followed by the removal of inorganic salts gave 1,1 0 -bis(dichlorophosphino)ferrocene (6) in good yield. The treatment of 6 with two molar amounts of LiP(H)Ar (Ar ¼ Tbt (7a) or Bbt (7b)), which was prepared by the reaction of H 2 PAr (Ar ¼ Tbt (4a) or Bbt (4b)) with an equimolar amount of butyllithium in ether at À40 C, in benzene at room temperature gave the corresponding chlorohydrodiphosphane derivatives as diastereomixtures.…”

Section: Resultsmentioning

confidence: 99%

“…4h, 6 The 31 P NMR spectral data of several (E)-diphosphenes and (E)-ferrocenyldiphosphenes are shown in Table 2 as references.…”

Section: Resultsmentioning

confidence: 99%

“…1.854(4) C(31)-P(2)-P(1) 101.9(3) P(2)-C(31) 1.807 (6) (E,E)-8a P-P 2.055 C(Dmp)-P-P 99.8 C(Dmp)-P-P-C(Cp) À179:2 P-C(Dmp) 1.860 C(Cp)-P-P 102.9 P-C(Cp) 1.819…”

Section: Resultsmentioning

confidence: 99%

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Kinetically Stabilized 1,1′-Bis[(E)-diphosphenyl]ferrocenes: Syntheses, Structures, Properties, and Reactivity

Nagahora¹,

Sasamori²,

Watanabe³

et al. 2007

Bulletin of the Chemical Society of Japan

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Kinetically stabilized 1,1 0 -bis[(E)-diphosphenyl]ferrocenes were synthesized by taking advantage of extremely bulky substituents, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (denoted as Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (denoted as Bbt) groups, and characterized by the spectroscopic and X-ray crystallographic analyses. The electronic structures of the 1,1 0 -bis[(E)-diphosphenyl]ferrocenes were determined by analyzing electronic spectra, the transitions of which were reasonably assigned based on theoretical calculations. In the cyclic voltammograms, there were two well-defined reversible one-electron reduction couples corresponding to the intramolecular two diphosphene units. Furthermore, the 1,1 0 -bis[(E)-diphosphenyl]ferrocene was found to undergo ligand-exchange reactions with group 6 metal carbonyl complexes along with the E-to-Z isomerization of the diphosphene moieties, leading to the formation of the corresponding 1,1 and W). The molecular structures of these complexes were determined by spectroscopic analyses ( 1 H, 13 C, and 31 P NMR spectra, and UV-vis spectra), and that of the tungsten complex was determined by X-ray crystallographic analysis. Several types of d ! Ã P=P electron transitions due to the iron and group 6 metals were detected by using UV-vis spectroscopy, and these results were supported by theoretical calculations.The chemistry of heavier congeners of azo-compound (-N=N-) has been studied extensively for more than 25 years, 1 since the pioneering synthesis and isolation of the first stable diphosphene bearing 2,4,6-tri-tert-butylphenyl groups (Mes Ã P=PMes Ã ), reported by Yoshifuji and co-workers. Nowadays, it is well-known that diphosphenes, which have relatively low-lying Ã orbitals, readily undergo one-electron reduction to give their anion-radical species. 3 We have reported the synthesis of novel doubly bonded systems between heavier group 15 elements (dipnictenes), that is, diphosphene, distibene (-Sb=Sb-), dibismuthene (-Bi=Bi-), phosphabismuthene (-P=Bi-), and stibabismuthene (-Sb=Bi-), by taking advantage of bulky protecting groups, such as 2,4,6-tris[bis-(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) groups (Fig. 1). 4 Furthermore, the redox properties of (E)-BbtE=EBbt (E ¼ P, Sb, and Bi) have been systematically elucidated based on cyclic voltammetry and DFT calculations, and the solidstate structure of the first stable anion radical species of (E)-BbtSb=SbBbt has also been reported. 4i,4k Low-coordinated species of heavier group 15 elements have attracted much interest due to their low-lying Ã levels compared with diazenes (-N=N-) from two reasons: (i) their electrochemical properties 3 and (ii) coordination ability toward transition metals. (Fig. 2), and its absorption band 1884 Bull. Chem. Soc. Jpn. Vol. 80, No. 10, 1884-1900 (2007 Ó 2007 The Chemical Society of Japan BCSJ Award Article

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Section: Complexsupporting

confidence: 52%

Section: Resultsmentioning

confidence: 99%

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Kinetically Stabilized 1,1′-Bis[(E)-diphosphenyl]ferrocenes: Syntheses, Structures, Properties, and Reactivity

Nagahora¹,

Sasamori²,

Watanabe³

et al. 2007

Bulletin of the Chemical Society of Japan

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“…87 This appears also to be true for the ferrocenyldiphosphene 128 in eq 35. 229 The stereochemistry of adduct 129 is not definitely established, but a head-to-head dimer is spectroscopically made plausible. More importantly, however, the ferrocenyl substituent obviously is responsible for a ready thermal cycloreversion to the original diphosphene.…”

Section: B [2+2] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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Synthesis of Multiply Bonded Phosphorus Compounds Using Silylphosphines and Silylphosphides

Yoshifuji

Toyota

2009

Patai's Chemistry of Functional Groups

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Introduction Survey of Silylphosphines and Alkali Metal Silylphosphides Disilyl(2,4,6‐tri‐ t ‐Butylphenyl)Phosphines Monosilyl(2,4,6‐tri‐ t ‐Butylphenyl)Phosphines Alkali Metal Monosilyl(2,4,6‐tri‐ t ‐Butylphenyl) Phosphides Phosphasilenes

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Synthesis, Spectroscopic Properties, and Reactivity of Ferrocenyl(2,4,6-tri-tert-butylphenyl)diphosphene

Cited by 49 publications

References 16 publications

Kinetically Stabilized 1,1′-Bis[(E)-diphosphenyl]ferrocenes: Syntheses, Structures, Properties, and Reactivity

Kinetically Stabilized 1,1′-Bis[(E)-diphosphenyl]ferrocenes: Syntheses, Structures, Properties, and Reactivity

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

Synthesis of Multiply Bonded Phosphorus Compounds Using Silylphosphines and Silylphosphides

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