Zwitterionic Stabilization of a Reactive Cobalt Tris‐Isocyanide Monoanion by Cation Coordination

Carpenter, Alex E.; Margulieux, Grant W.; Millard, Matthew D.; Moore, Curtis E.; Weidemann, Nils; Rheingold, Arnold L.; Figueroa, Joshua S.

doi:10.1002/anie.201205058

Cited by 62 publications

(68 citation statements)

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“…[1] While coordination complexes with subvalent oxidation states are not uncommon for late transition metals such as Fe and Co (for example,Fe ÀI/ÀII and Co ÀI ), [2] much less is known about the analogous oxidation states for Ni. [1] While coordination complexes with subvalent oxidation states are not uncommon for late transition metals such as Fe and Co (for example,Fe ÀI/ÀII and Co ÀI ), [2] much less is known about the analogous oxidation states for Ni.…”

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“…Of relevance,f ormal Cu 0 complexes,C u(TPB) and Cu(Me 2 -cAAC) 2 ,h ave also been isolated ( Figure 1a;T PB = trisphoshinoborane,c AAC = cyclic alkyl amino carbene). [6] Theunpaired spin in these molecules is delocalized across the Cu À Band C À Cu À Cbonds,with dominant radical character at the Ba nd Ca toms,r espectively.W es ought to target isoelectronic nickelate complexes using our previously reported NiML complexes (L = [N(o-NCH 2 P i Pr 2 )C 6 H 4 ] 3À ; M = Al (1), Ga (2), In), in which the Ni center is zerovalent with ad 10 electron count.…”

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Formal Nickelate(−I) Complexes Supported by Group 13 Ions

et al. 2018

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Formal nickelate(-I) complexes bearing Group 13 metalloligands (M=Al and Ga) were isolated. These 17 e complexes were synthesized by one-electron reduction of the corresponding Ni →M precursors, and were investigated by single-crystal X-ray diffraction, EPR spectroscopy, and quantum chemical calculations. Collectively, the experimental and computational data support: 1) the strengthening of the Ni-M bond upon one-electron reduction, and 2) the delocalization of the unpaired spin across the Ni and M atoms. An intriguing electronic configuration is revealed where three valence electrons occupy two σ-type bonding interactions: Ni(3dz2 ) →M and σ-(Ni-M) . The latter is an unusual Ni-M σ-bonding molecular orbital that comprises primarily the Ni 4p and M np /ns atomic orbitals.

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Formal Nickelate(−I) Complexes Supported by Group 13 Ions

et al. 2018

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“…[1] While binding of O 2 to transition metals has al ong history, [2] coordination of N 2 to transition metals was not observed until 1965, likely due to the weak s-donating and poor p-accepting nature of N 2 . [4] Dinitrogen complexes for Co, [5] Ni, [6] and especially Cu [7] are less common than for the early to middle transition metals aresult of the weaker p-backbonding to N 2 at Co,Ni, and Cu centers.M uch more easily reduced, dioxygen often binds at metal fragments capable of stabilizing dinitrogen complexes despite the specific electronic differences in M À O 2 and M À N 2 bonding. [4] Dinitrogen complexes for Co, [5] Ni, [6] and especially Cu [7] are less common than for the early to middle transition metals aresult of the weaker p-backbonding to N 2 at Co,Ni, and Cu centers.M uch more easily reduced, dioxygen often binds at metal fragments capable of stabilizing dinitrogen complexes despite the specific electronic differences in M À O 2 and M À N 2 bonding.…”

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A Dinitrogen Dicopper(I) Complex via a Mixed‐Valence Dicopper Hydride

et al. 2016

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Low-temperature reaction of the tris(pyrazolyl)borate copper(II) hydroxide [(iPr2) TpCu]2 (μ-OH)2 with triphenylsilane under a dinitrogen atmosphere gives the bridging dinitrogen complex [(iPr2) TpCu]2 (μ-1,2-N2 ) (3). X-ray crystallography reveals an only slightly activated N2 ligand (N-N: 1.111(6) Å) that bridges between two monovalent (iPr2) TpCu fragments. While DFT studies of mono- and dinuclear copper dinitrogen complexes suggest weak π-backbonding between the d(10) Cu(I) centers and the N2 ligand, they reveal a degree of cooperativity in the dinuclear Cu-N2 -Cu interaction. Addition of MeCN, CNAr(2,6-Me) , or O2 to 3 releases N2 with formation of (iPr2) TpCu(L) (L=NCMe, CNAr(2,6-Me2) ) or [(iPr2) TpCu]2 (μ-η(2) :η(2) -O2 ) (1). Addition of triphenylsilane to [(iPr2) TpCu]2 (μ-OH)2 in pentane allows isolation of a key intermediate [(iPr2) TpCu]2 (μ-H) (5). Although 5 thermally decays under N2 to give 3, it reduces unsaturated substrates, such as CO and HC≡CPh to HC(O)H and H2 C=CHPh, respectively.

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“…[14] While the oligomeric members of [Pt 3 (CO) 6 ] n 2À with n = 2-8 have all been isolated and structurally characterized, [7][8][9][10][11]15] the parent species [Pt 3 (CO) 6 ] 2À (n = 1) has eluded complete characterization. [21] Given our success in isolating isocyano analogues to classical carbonyl metalates using sterically encumbering m-terphenyl isocyanides, [22][23][24][25] we report herein the synthesis and structural characterization of K 2 [Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ]( Ar Dipp2 = 2,6-(2,6-(i-Pr) 2 C 6 H 3 ) 2 C 6 H 3 ), as well as the open-shell monoanion K[Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ]. [21] Given our success in isolating isocyano analogues to classical carbonyl metalates using sterically encumbering m-terphenyl isocyanides, [22][23][24][25] we report herein the synthesis and structural characterization of K 2 [Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ]( Ar Dipp2 = 2,6-(2,6-(i-Pr) 2 C 6 H 3 ) 2 C 6 H 3 ), as well as the open-shell monoanion K[Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ].…”

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Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

2016

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Owing to their unique topologies and abilities to selfassemble into av ariety of extended and aggregated structures, the binary platinum carbonyl clusters [Pt 3 (CO) 6 ] n 2À ("Chini clusters") continue to draw significant interest. Herein, we report the isolation and structural characterization of the trinuclear electron-transfer series [Pt 3 (m-CO) 3 (CNAr Dipp2 ) 3 ] nÀ (n = 0, 1, 2), which represents au nique set of monomeric Pt 3 clusters supported by p-acidic ligands.S pectroscopic,c omputational, and synthetic investigations demonstrate that the highest-occupied molecular orbitals of the mono-and dianionic clusters consist of acombined p*-framework of the CO and CNAr Dipp2 ligands,w ith negligible Pt character.A ccordingly,t his study provides precedent for an ensemble of carbonyl and isocyanide ligands to function in ar edox noninnocent manner.

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Zwitterionic Stabilization of a Reactive Cobalt Tris‐Isocyanide Monoanion by Cation Coordination

Cited by 62 publications

References 50 publications

Formal Nickelate(−I) Complexes Supported by Group 13 Ions

Formal Nickelate(−I) Complexes Supported by Group 13 Ions

A Dinitrogen Dicopper(I) Complex via a Mixed‐Valence Dicopper Hydride

Monomeric Chini‐Type Triplatinum Clusters Featuring Dianionic and Radical‐Anionic π*‐Systems

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