Highly reduced organometallics. 6. Synthesis and chemistry of tricarbonylphosphineferrates(2-), Fe(CO)3PR32-

Chen, Yu Sen; Ellis, John E.

doi:10.1021/ja00368a059

Cited by 15 publications

(10 citation statements)

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“…When this tight ion pair is perturbed by addition of a crown ether, or [PPN] + Cl − , increasing electron density at Fe facilitates loss of the PPh 3 ligand and the resulting 16-electron system scavenges CO to produce the dicarbonyl anion. Such loss of the poorer π-acceptor is consistent with observations by Chen and Ellis upon reduction of metal complexes containing both CO and PR 3 . The fate of the Fe atom that was the source of the second CO is not clear at this time.…”

Section: Resultssupporting

confidence: 86%

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R

et al. 2009

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A new transition metalate system, [(η 5 -Me 3 SiC 5 H 4 )Fe(CO)(PPh 3 )] -M þ (SiFpPM; M = Li, Na), was synthesized via treatment of (η 5 -C 5 H 5 )Fe(CO)(PPh 3 )SiMe 3 with sodium and lithium diisopropylamides (MN(iPr 2 ); NADA and LDA, respectively). The utility of NADA was far superior to that of LDA, with shorter reaction times, lower reagent concentrations, and higher yields. Infrared spectroscopic analysis of the new ferrates indicated that their stability and utility were dependent upon the tight ion pairs Fe-CO-M; in the presence of coordinating solvents and ionophores the separated ion pairs formed led to the expulsion of the PPh 3 and CO scavenging led to formation of the dicarbonylferrate [(η 5 -Me 3 SiC 5 H 4 )Fe(CO) 2 ] -M þ . Hexane was the solvent of choice for formation and use of the ferrates. Reactions of the new ferrates with MeI led to [SiFpP]CH 3 , whereas reactions with ClCH 2 SiMe 2 R (R = H, SiMe 3 ) did not lead to the expected Fe-C bonded complexes [SiFpP]CH 2 SiMe 2 R but to high yields of the rearranged complexes [SiFpP]SiMe 2 CH 2 R. The presence of the thermally labile phosphine group readily produces a coordinatively unsaturated 16e species that permits Fe-CH 2 -SiMe 2 R to FeSiMe 2 CH 2 R rearrangements (previously observed photochemically with the simple Fp derivatives) to occur thermally.

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Section: Resultssupporting

confidence: 86%

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R

et al. 2009

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“…Mass Spectrom., 8, 1729 (1980). (8) Our results are in agreement with those reported for [C7Hg]+• isomers by F. W. McLafferty, R. Kornfield, W. F. Haddon, K. Levsen, I. Sakai, P. E. Bente, S.-C. Tsai, and H. D. R. Schuddemage, J. Am.…”

supporting

confidence: 92%

“…We have measured7 the collisional activation spectra of the toluene molecular ion and the mjz 92 product ion from benzyl ethyl ether and observed significant differences in the m/z 75-78 region of the two spectra. 8 Either the m/z 92 ion formed is not the toluene radical cation or the toluene radical cation is formed initially and rearranges at least partially prior to collision.…”

mentioning

confidence: 99%

Mechanistic studies of unimolecular ionic decompositions by deuterium and heavy-atom isotope effects. Concerted elimination of acetaldehyde from the benzyl ethyl ether radical cation

Stone¹,

Bowie²,

Underwood³

et al. 1983

J. Am. Chem. Soc.

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“…[29] In addition, Ellis and coworkers developed a straightforward route for the synthesis of [Fe(CO) 3 (PR 3 )] 2À dianion (PR 3 = PPh 3 , PhPMe 2 , and PMe 3 ) via the deprotonation of the corresponding metal carbonyl hydrides, [HFe(CO) 3 (PR 3 )] À , which was generated by treating Fe(CO) 4 (PR 3 ) with a methanolic solution of hydroxide. [30] However, each step of this method required excess amounts of reagents ([Et 4 N]OH and K[sec-Bu 3 BH]). We propose an alternative approach involving the reduction of an Fe(0) precursor with a P,N-bidentate ligand, resulting in the formation of an Fe(-II) complex and the simultaneous dissociation of the appended amino group (Figure 1, c).…”

Section: Introductionmentioning

confidence: 99%

Reactivity of an Iron Carbonyl Dianion Dictated by a Lewis Basic Appendant

Zhang,

Guo,

Chu

2024

Eur J Inorg Chem

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Studies toward transition metals in negative oxidation states are much less explored compared to those in zero or positive oxidation states. In this study, we present the synthesis and reactivity studies of an Fe(‐II) carbonyl dianion (3) featuring an appended Lewis base, [(L)Fe(CO)3]2‐ (L=Ph2PCH2CH2NMe2). Unlike the well‐known reactivity of [Fe(CO)4]2‐ with common electrophiles (E+) which typically forms [(E)2Fe(CO)4], 3 reacted with 2 equiv. of Ph3SnCl to afford a mixture of two products: one being an Fe(II) bis(triphenylstannyl) product (4), and the other an Fe stannylene product (5). Further insights into the reactivity of 3 was elucidated through its reactions with 2 equiv. of Cy3SnCl or Me3SiCl, producing an Fe(II) bis(tricyclohexylstannyl) product (8) and a zwitterionic complex (11), respectively, the latter emerging via THF ring‐opening. Intermediates generated from reactions of 3 with 1 equiv. of each electrophile were isolated to shed light on the reaction mechanisms, highlighting the influence of appended Lewis base on the reactivity of metal carbonyl dianions, especially the generation of the novel stannylene complex 5. The electronic structure of this paramagnetic stannylene complex was also investigated by computational studies.

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Highly reduced organometallics. 6. Synthesis and chemistry of tricarbonylphosphineferrates(2-), Fe(CO)3PR32-

Cited by 15 publications

References 1 publication

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R

Mechanistic studies of unimolecular ionic decompositions by deuterium and heavy-atom isotope effects. Concerted elimination of acetaldehyde from the benzyl ethyl ether radical cation

Reactivity of an Iron Carbonyl Dianion Dictated by a Lewis Basic Appendant

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Highly reduced organometallics. 6. Synthesis and chemistry of tricarbonylphosphineferrates(2-), Fe(CO)3PR32-

Cited by 15 publications

References 1 publication

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η5-Me3SiC5H4)Fe(CO)(PPh3)]−Na+(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH2SiMe2R (R = H, SiMe3) to SiFpP−SiMe2CH2R

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η5-Me3SiC5H4)Fe(CO)(PPh3)]−Na+(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH2SiMe2R (R = H, SiMe3) to SiFpP−SiMe2CH2R

Mechanistic studies of unimolecular ionic decompositions by deuterium and heavy-atom isotope effects. Concerted elimination of acetaldehyde from the benzyl ethyl ether radical cation

Reactivity of an Iron Carbonyl Dianion Dictated by a Lewis Basic Appendant

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The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R

The Utility of Sodium Diisopropylamide (NADA): Formation of a New Transition Metalate via Silyl Migration Chemistry, [(η⁵-Me₃SiC₅H₄)Fe(CO)(PPh₃)]⁻Na⁺(SiFpPNa), and Resulting Thermal Rearrangements of the Complexes SiFpP−CH₂SiMe₂R (R = H, SiMe₃) to SiFpP−SiMe₂CH₂R