Formation of a Stannyl Amido Complex by the Reaction of a Terminal Iridium Nitrido Complex with a Stannane

Sieh, Daniel; Burger, Peter

doi:10.1002/zaac.201400235

Cited by 7 publications

(3 citation statements)

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“…27 Moreover, this geometry exists in transition-metal dinitrogen and nitrido complexes supported by PEP pincer ligands some of which have successfully been employed in studies of synthetic nitrogen fixation. 8,[31][32][33][34] Weiss and co-workers presented bis(dinitrogen) complexes with two κ 2 -coordinated PNP ligands in which the nitrogen atoms mediate proton transfer to the N 2 ligands. 28 Besides the nature of the central atom (N vs. P), a second important property of tridentate PEP ligands is the chain length of the aliphatic linkages.…”

Section: Introductionmentioning

confidence: 99%

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂

et al. 2016

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The syntheses of molybdenum dinitrogen complexes supported by the tridentate PEP ligands (E = N, P) prPP(Ph)P = (Ph2PCH2CH2CH2)2P(Ph), prPPHP = (Ph2PCH2CH2CH2)2PH, PN(Ph)P = (Ph2PCH2CH2)2N(Ph) and prPN(Ph)P = (Ph2PCH2CH2CH2)2N(Ph) are reported. Together with the coligand dmpm = (CH3)2PCH2P(CH3)2 dinitrogen complexes of the type [Mo(N2)(PEP)(dmpm)] are formed. The new systems are characterized by IR and NMR spectroscopy and compared with the literature-known complex [Mo(N2)(dpepp)(dmpm)] (1) (dpepp = PhP(CH2CH2PPh2)2). The consequences of the substitution of the central P-donor of dpepp by N and the replacement of its C2 by C3 linkages as well as the exchange of the EPh by an EH function are investigated with respect to the stability of the corresponding N2-complexes. Importantly, the activation of the N2 ligand drastically increases upon replacing the trans-phosphine with a trans-amine donor.

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Section: Introductionmentioning

confidence: 99%

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂

et al. 2016

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“…The conversion of mononuclear (PBD)IrN to Ir–NH 2 (PBD = 2,6-(2,6- i Pr 2 C 6 H 3 –NCMe) 2 C 5 H 3 N) was achieved via hydrogenation of the corresponding nitride species with dihydrogen , and, more recently, via hydrostannylation followed by hydrolysis . Additionally, the transient nitride species NRu 2 (D(3,5-Cl 2 )PhF) 3 , where (D(3,5-Cl 2 )PhF = N , N ′-bis(3,5-dichlorophenyl)formamidinate), , ( iPr PDI)CoN ( iPr PDI = 2,6-(ArNCPh) 2 C 5 H 3 N; i Pr = 2,6- i Pr 2 C 6 H 3 ), and (C 5 Me 5 ) 2 UN(N(SiMe 3 ) 2 ) have been implicated in the formation of metal–amido via intramolecular C–H activation.…”

Section: Resultsmentioning

confidence: 99%

Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

et al. 2015

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In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)V≡N(X)] formulation [nacnac = (Ar)NC(Me)CHC(Me)(Ar)(-), Ar = 2,6-(CHMe2)2C6H3); X(-) = OAr (1) and N(4-Me-C6H4)2 (Ntolyl2) (2)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H2SiPh2, readily converts the nitride ligand in 1 into a primary silyl-amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)V{N(H)SiHPh2}(OAr)] (3). Likewise, addition of the B-H bond in pinacolborane to the nitride moiety in 2 results in formation of the boryl-amide complex [(nacnac)V{N(H)B(pinacol)}(Ntolyl2)] (4). In addition to spectroscopic data, complexes 3 and 4 were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of 1 with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na]2[(nacnac)V(N)(OAr)]2 (5), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies.

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“…11 We reported on an electron-rich iridium nitrido complex 1 (Scheme 1) that is competent in dihydrogen 30 and intramolecular C−H bond activation 27 and forms an unprecedented monostannylamido complex upon the addition of Ph 3 SnH. 34 Despite the electrophilic nature of the nitrido ligand proposed for the reaction with dihydrogen and trimethylamine-N-oxide, which leads to the nitrosyl complex, 30,35 we could demonstrate a nucleophilic pathway in the activation of Si−H bonds in triarylsilanes, 36,37 indicating the ambiphilic nature of the nitrido ligand in complex 1. The ambiphilic nature of the nitrido ligand in the iridium nitrido complex 1 led us to explore its redox chemistry and the possibility to make the nitrido nitrogen atom more electrophilic by oxidation.…”

Section: Introductionmentioning

confidence: 99%

Cleavage of an Aromatic C–C Bond in Ferrocene by Insertion of an Iridium Nitrido Nitrogen Atom

Schiller,

Sieh,

Lindenmaier

et al. 2023

J. Am. Chem. Soc.

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The intermolecular cleavage of C–C bonds is a rare event. Herein, we report on a late transition-metal terminal nitrido complex, which upon oxidation undergoes insertion of the nitrido nitrogen atom into the aromatic C–C bond of ferrocene. This reaction path was confirmed through 15N and deuterium isotope labeling experiments of the nitrido complex and ferrocenium, respectively. Cyclic voltammetry and UV/vis spectroscopy monitoring of the reaction revealed that oxidation is the initial step, yielding the tentative radical cationic nitrido complex, which is experimentally supported by extended X and Q-band electron paramagnetic resonance (EPR) and ENDOR, UV/vis, vT 1H NMR, and vibrational spectroscopic data. Density functional theory (DFT) and multireference calculations of this highly reactive intermediate revealed an S = 1/2 ground state. The high reactivity can be traced to the increased electrophilicity in the oxidized complex. Based on high-level PNO-UCCSD(T) calculations and UV/vis kinetic measurements, it is proposed that the reaction proceeds by initial electrophilic exo attack of the nitrido nitrogen atom at the cyclopentadienyl ring and consecutive ring expansion to a pyridine ring.

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Formation of a Stannyl Amido Complex by the Reaction of a Terminal Iridium Nitrido Complex with a Stannane

Abstract: Abstract. The chemistry of low valent late transition metal complexes with a terminal nitrido unit still is a growing field and only few reactions have been studied so far. We have tested the reactivity of a pseudo square planar iridium nitrido complex against triphenyl tin hy-

Cited by 7 publications

References 42 publications

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂

Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

Cleavage of an Aromatic C–C Bond in Ferrocene by Insertion of an Iridium Nitrido Nitrogen Atom

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Formation of a Stannyl Amido Complex by the Reaction of a Terminal Iridium Nitrido Complex with a Stannane

Abstract: Abstract. The chemistry of low valent late transition metal complexes with a terminal nitrido unit still is a growing field and only few reactions have been studied so far. We have tested the reactivity of a pseudo square planar iridium nitrido complex against triphenyl tin hy-

Cited by 7 publications

References 42 publications

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N2

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N2

Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

Cleavage of an Aromatic C–C Bond in Ferrocene by Insertion of an Iridium Nitrido Nitrogen Atom

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Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂

Molybdenum dinitrogen complexes facially coordinated by linear tridentate PEP ligands (E = N or P): impact of the central E donor in trans-position to N₂