COMPOUNDS WITH Zn–Zn AND Mg–Mg BONDS

Peloso, Riccardo; Resa, Irene; Rodríguez, Amor; Carmona, Ernesto; Freitag, Kerstin; Jones, Cameron; Stasch, Andreas; Boutland, Aaron J.; Lips, Felicitas

doi:10.1002/9781119477822.ch3

Cited by 7 publications

(5 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…To test this hypothesis the very hindered magnesium( i ) complex [{( TCHP Nacnac)Mg} 2 ] ( TCHP Nacnac = [{(TCHP)NCMe} 2 CH] − , TCHP = 2,4,6-tricyclohexylphenyl) 5 was prepared in good isolated yield, by reduction of a toluene/diethyl ether solution of [( TCHP Nacnac)MgI(OEt 2 )] over a sodium mirror (see ESI † for full details). 12 However, subsequent treatment of 5 with one equivalent of either DMAP or the NHC, :C{(MeNCMe) 2 }, led to no reaction, presumably due to steric inaccessibility of its Mg centres, as is evident from its molecular structure ( Fig. 1a ).…”

Section: Resultsmentioning

confidence: 99%

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…For example, the o ‐CH 3 of the mesityl group are shifted from δ 1.91 ppm in [( Mes BDI−Mg) 2 ] to δ 2.53 ppm in complex 3 . [37] The 31 P{ 1 H} NMR spectrum confirms the formation of a [P 10 ] 4− moiety by the presence of four resonances at δ −30.6 (br, Δν 1/2 ≈600 Hz), 24.5 (br, Δν 1/2 ≈550 Hz), 126.5 (br, Δν 1/2 ≈500 Hz), and 152.1 (br, Δν 1/2 ≈500 Hz) ppm. Unfortunately, the P−P coupling constants could not be determined as finely resolved 31 P{ 1 H} NMR spectra could not be obtained even at low temperature (‐80 °C) due to the low solubility of 3 at low temperatures and the fluxional behaviour of the [P 10 ] 4− fragment (Figure S12‐13).…”

Section: Resultsmentioning

confidence: 73%

“…For example, the o-CH 3 of the mesityl group are shifted from δ 1.91 ppm in [( Mes BDIÀ Mg) 2 ] to δ 2.53 ppm in complex 3. [37] The 31 P{ 1 H} NMR spectrum confirms the formation of a [P 10 ] 4À moiety by the presence of four resonances at δ À 30.6…”

Section: Magnesium Polyphosphidesmentioning

confidence: 77%

A Structural Diversity of Molecular Alkaline‐Earth‐Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

Yadav

Weber

Singh

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

A series of molecular group 2 polyphosphides has been synthesized by using air-stable [Cp*Fe(η 5 -P 5 )] (Cp* = C 5 Me 5 ) or white phosphorus as polyphosphorus precursors. Different types of group 2 reagents such as organomagnesium, mono-valent magnesium, and molecular calcium hydride complexes have been investigated to activate these polyphosphorus sources. The organo-magnesium complex [( Dipp BDIÀ Mg(CH 3 )) 2 ] ( Dipp BDI = {[2,6-i Pr 2 C 6 H 3 NCMe] 2 CH} À ) reacts with [Cp*Fe(η 5 -P 5 )] to give an unprecedented Mg/Fesupramolecular wheel. Kinetically controlled activation of [Cp*Fe(η 5 -P 5 )] by different mono-valent magnesium complexes allowed the isolation of Mg-coordinated formally mono-and di-reduced products of [Cp*Fe(η 5 -P 5 )]. To obtain the first examples of molecular calcium-polyphosphides, a molecular calcium hydride complex was used to reduce the aromatic cyclo-P 5 ring of [Cp*Fe(η 5 -P 5 )]. The Ca-Fe-polyphosphide is also characterized by quantum chemical calculations and compared with the corresponding Mg complex. Moreover, a calcium coordinated Zintl ion (P 7 ) 3À was obtained by molecular calcium hydride mediated P 4 reduction.

show abstract

“…Method A: Complex [Mo 2 (H) 2 (μ-Ad Dipp2 ) 2 (thf) 2 ] ( 1 ; 30 mg, 0.03 mmol) and ZnCp 2 * (10 mg, 0.03 mmol) were dissolved in toluene (3 mL) at room temperature inside the glovebox and transferred to an ampule. After stirring for 8 h at 60 °C, toluene was removed under a vacuum, and diethyl ether was added.…”

Section: Methodsmentioning

confidence: 99%

Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C₅Me₅)ZnH and (C₅Me₅)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex

et al. 2022

Self Cite

View full text Add to dashboard Cite

Heterobimetallic complexes containing M−C−E linkages (M = transition metal atom; E = main group metal) have been postulated as relevant intermediates in cross-coupling reactions. Despite this, structural data for these species are scarce. In this contribution, we explore the coordination of E−C bonds (E = Zn, Mg, Al) to the Mo atoms of dimolybdenum complexes containing quadruple Mo−Mo bonds. In addition, the reactivity of the bis(hydride) [Mo 2 (H) 2 (μ-Ad Dipp2 ) 2 (thf) 2 ] complex (Ad Dipp2 = HC[N(2,6-i Pr 2 C 6 H 3 )] 2 ) with the zincocenes Zn(C 5 Me 5 ) 2 and Zn 2 (η 5 -C 5 Me 5 ) 2 reveals the formation of dimolybdenum compounds in which (C 5 Me 5 )Zn−H and (C 5 Me 5 )ZnZn−H bonds bind to the trans-H−Mo≣Mo−H core. DFT calculations and an NBO analysis disclose a general bonding mechanism for the reported H−Mo≣Mo−E−R rings that is consistent with the penetration indices of the different atom pairs. The bonding comprises three center−two electron Mo−H−E and Mo−R−E bonds supplemented by π-coordination of the Mo≣Mo bond to the electropositive metal E.

show abstract

COMPOUNDS WITH Zn–Zn AND Mg–Mg BONDS

Cited by 7 publications

References 37 publications

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

A Structural Diversity of Molecular Alkaline‐Earth‐Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C₅Me₅)ZnH and (C₅Me₅)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex

Contact Info

Product

Resources

About

COMPOUNDS WITH Zn–Zn AND Mg–Mg BONDS

Cited by 7 publications

References 37 publications

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

A Structural Diversity of Molecular Alkaline‐Earth‐Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C5Me5)ZnH and (C5Me5)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex

Contact Info

Product

Resources

About

Coordination of E–C Bonds (E = Zn, Mg, Al) and the Zn–H Bonds of (C₅Me₅)ZnH and (C₅Me₅)ZnZnH across a Quadruply Bonded Dimolybdenum Dihydride Complex