Reduction of tungsten complexes with primary phosphines and lithium dialkyl phosphides. X-ray crystal structures of [(Cp*WCl2)2·(t-Bu2PPt-Bu2)2], [(Cp*WCl4)(H2PPh)], [{(PhN)WCl2(PMe3)2} 2(μ-N2)] and trans-WCl4(H2Pt-Bu)2 (Cp* = η5-C5Me5)

Harlan, C. Jeff; Jones, Richard A.; Koschmieder, Stefan U.; Nunn, Christine M.

doi:10.1016/s0277-5387(00)80274-0

Cited by 37 publications

(12 citation statements)

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“…Subsequent to these reports, the bis(dichlorotungsten) analog [WCl 2 (PMe 3 ) 3 ] 2 (μ-1,2-N 2 ), 95-2Cl , the bis(trichlorotungsten) [WCl 3 (PMe 3 ) 2 ] 2 (μ-1,2-N 2 ), 95-3Cl , the bis(tricarbonyltungsten) [W(CO) 3 (P i Pr 3 ) 2 ] 2 (μ-1,2-N 2 ), 95-CO , and [(PhN)Cl 2 (PMe 3 ) 2 W] 2 (μ-N 2 ), 95-NPh , were obtained (Figure ). The first two were reported by Harvey et al, the carbonyl complex from Kubas and workers, and the imide by Harlan et al − The long N–N bonds observed in 95-2Cl (1.279(4) Å) and 95-3Cl (1.24(2) Å) as compared to 95-CO (1.136(6) Å with ν NN = 1939 cm –1 ) bear strong resemblance with the greater N–N bond activation observed upon removal of CO ligand from 88-Mo/CO . The N–N bond in 95-NPh (1.19(2) Å) is of comparable length to that of 95-CO , highlighting again the discounting effect of ancillary π-acids on N 2 activation.…”

Section: Dinitrogen Activation By Multimetallic Complexesmentioning

confidence: 78%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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Activation of dinitrogen plays an important role in daily anthropogenic life, and the processes by which this fixation occurs have been a longstanding and significant research focus within the community. One of the major fields of dinitrogen activation research is the use of multimetallic compounds to reduce and/or activate N2 into a more useful nitrogen-atom source, such as ammonia. Here we report a comprehensive review of multimetallic-dinitrogen complexes and their utility toward N2 activation, beginning with the d-block metals from Group 4 to Group 11, then extending to Group 13 (which is exclusively populated by B complexes), and finally the rare-earth and actinide species. The review considers all polynuclear metal aggregates containing two or more metal centers in which dinitrogen is coordinated or activated (i.e., partial or complete cleavage of the N2 triple bond in the observed product). Our survey includes complexes in which mononuclear N2 complexes are used as building blocks to generate homo- or heteromultimetallic dinitrogen species, which allow one to evaluate the potential of heterometallic species for dinitrogen activation. We highlight some of the common trends throughout the periodic table, such as the differences between coordination modes as it relates to N2 activation and potential functionalization and the effect of polarizing the bridging N2 ligand by employing different metal ions of differing Lewis acidities. By providing this comprehensive treatment of polynuclear metal dinitrogen species, this Review aims to outline the past and provide potential future directions for continued research in this area.

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Section: Dinitrogen Activation By Multimetallic Complexesmentioning

confidence: 78%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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“…However, most (η-C 5 R 5 )MXY compounds are dimeric. A few, for example [(η-C 5 Me 4 Et)V] 2 (μ-Br) 4 , ,,, {[(η-C 6 H 3 Me 3 )Nb] 2 (μ-I) 4 } n + ( n = 0, 1), [(η-C 5 Me 5 )Ta] 2 (μ-Br) 4 , [(η-C 5 Me 5 )W] 2 (μ-Cl) 4 , and several [(η-C 5 R 5 )Mo] 2 (μ-X) 4 (X = halogen), ,,,− adopt the structure 2a . The majority adopt the structure 2b , for example, [(η-C 5 H 2 (SiMe 3 ) 3 )TiCl(μ-O)] 2 , [(η-C 5 Me 5 )MX(μ-Cl)] 2 (X = Cl; M = Cr, ,, Re, Ru, , Rh, Ir; X = Me; M = Cr , ), [(η-C 5 R 5 )M(O)(μ-O)] 2 (M = Cr, Mo ), and [(η-C 5 R 5 )M(E 1 )(μ-E 2 )] 2 (M = Mo, W; E 1 = O, S; E 2 = S, Se − ).…”

Section: Resultsmentioning

confidence: 99%

Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C₅Me₅)V(μ-Cl)₂]₃

et al. 1997

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The cluster [(η-C5Me5)V(μ-Cl)2]3 was synthesized from VCl3(thf)3 and Bun 3SnC5Me5. It was oxidized by O2 to give (η-C5Me5)VCl2(O), and by NaN3 to give [(η-C5Me5)VCl(μ-N)]2. X-ray diffraction showed that [(η-C5Me5)V(μ-Cl)2]3 had an equilateral triangle of vanadium atoms (mean V−V 3.367 (2) Å), with each edge of the triangle symmetrically bridged by two chlorine atoms. The cluster contains six core electrons. The cluster [(η-C5Me5)V(μ-Cl2]3 had a magnetic moment of 2.92 μB at room temperature and showed antiferromagnetic behavior.

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“…26 Only in [Cl 2 W(NPh)(PMe 3 ) 2 ] 2 -(µ-N 2 ) was the N-N bond length (1.19(2) Å) comparable to that found in 1. 27 Interestingly, each of these compounds contained tungsten centers in high oxidation states compared to 1, in which the metal center is formally W(0). A more electron rich tungsten center should result in a more activated dinitrogen ligand due to a greater degree of WfN backbonding, 19b,d although this is clearly not the case with 1.…”

Section: Synthesis Crystal Structure and Reactivity Of A Tungstenmentioning

confidence: 99%

Comparison of H−H versus Si−H σ-Bond Coordination and Activation on 16e Metal Fragments. Organosilane, N₂, and Ethylene Addition to the Agostic Complex W(CO)₃(PR₃)₂and Dynamic NMR Behavior of the Latter

et al. 1997

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Variable-temperature (31)P{(1)H} NMR spectroscopy of the agostic complexes M(CO)(3)(PCy(3))(2) (M = Mo, W) indicates dynamic behavior as evidenced by collapse below -20 degrees C of a singlet to an AB signal plus a shifted singlet. The inequivalency of the phosphines is possibly due to the presence of conformational isomers resulting from hindered rotation of the M-P bond or, less likely, a geometric isomer with pseudo-cis PCy(3) ligands. Further studies on the coordination chemistry of W(CO)(3)(PR(3))(2) (R = iPr, Cy) were performed. The bridging dinitrogen complex [W(CO)(3)(PiPr(3))(2)](2)(&mgr;-N(2)) (1) was cleanly formed in the reaction of W(CO)(3)(PiPr(3))(2) with N(2). Complex 1 was structurally characterized and compared with other bridging dinitrogen compounds of tungsten. The ethylene complex W(CO)(3)(PCy(3))(2)(eta(2)-C(2)H(4)) (2) was synthesized and characterized by X-ray crystallography in order to compare the binding mode of ethylene with that of H(2). Phenylsilane reacted with W(CO)(3)(PR(3))(2) (R = iPr, Cy) to form the thermally unstable oxidative addition (OA) products WH(SiH(2)Ph)(CO)(3)(PR(3))(2) (3, R = Cy; 4, R = iPr). Diphenylsilane reacted with W(CO)(3)(PiPr(3))(2) at 60 degrees C to form the bridging silyl species [W(CO)(3)(PiPr(3))(&mgr;-SiHPh(2))](2) (5), which was confirmed by spectroscopic techniques and X-ray crystallography to have two 3-center 2-electron W.H.Si interactions. Detailed comparisons of the binding and activation of silanes versus H(2) on various 16e metal centers suggest a high degree of similarity, but relative ease of OA depends on the electrophilicity of the metal-ligand fragment and other factors such as bond energetics. Increasing the electrophilicity of the metal center (e.g., adding positive charge) may aid in stabilizing alkane coordination.

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Reduction of tungsten complexes with primary phosphines and lithium dialkyl phosphides. X-ray crystal structures of [(CpWCl2)2·(t-Bu2PPt-Bu2)2], [(CpWCl4)(H2PPh)], [{(PhN)WCl2(PMe3)2} 2(μ-N2)] and trans-WCl4(H2Pt-Bu)2 (Cp* = η5-C5Me5)

Cited by 37 publications

References 37 publications

Activation of Dinitrogen by Polynuclear Metal Complexes

Activation of Dinitrogen by Polynuclear Metal Complexes

Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C₅Me₅)V(μ-Cl)₂]₃

Comparison of H−H versus Si−H σ-Bond Coordination and Activation on 16e Metal Fragments. Organosilane, N₂, and Ethylene Addition to the Agostic Complex W(CO)₃(PR₃)₂and Dynamic NMR Behavior of the Latter

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Reduction of tungsten complexes with primary phosphines and lithium dialkyl phosphides. X-ray crystal structures of [(Cp*WCl2)2·(t-Bu2PPt-Bu2)2], [(Cp*WCl4)(H2PPh)], [{(PhN)WCl2(PMe3)2} 2(μ-N2)] and trans-WCl4(H2Pt-Bu)2 (Cp* = η5-C5Me5)

Cited by 37 publications

References 37 publications

Activation of Dinitrogen by Polynuclear Metal Complexes

Activation of Dinitrogen by Polynuclear Metal Complexes

Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C5Me5)V(μ-Cl)2]3

Comparison of H−H versus Si−H σ-Bond Coordination and Activation on 16e Metal Fragments. Organosilane, N2, and Ethylene Addition to the Agostic Complex W(CO)3(PR3)2and Dynamic NMR Behavior of the Latter

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Reduction of tungsten complexes with primary phosphines and lithium dialkyl phosphides. X-ray crystal structures of [(CpWCl2)2·(t-Bu2PPt-Bu2)2], [(CpWCl4)(H2PPh)], [{(PhN)WCl2(PMe3)2} 2(μ-N2)] and trans-WCl4(H2Pt-Bu)2 (Cp* = η5-C5Me5)

Organometallic Halides: Preparation and Physical and Chemical Properties of Tris[(η-pentamethylcyclopentadienyl)dichlorovanadium], [(η-C₅Me₅)V(μ-Cl)₂]₃

Comparison of H−H versus Si−H σ-Bond Coordination and Activation on 16e Metal Fragments. Organosilane, N₂, and Ethylene Addition to the Agostic Complex W(CO)₃(PR₃)₂and Dynamic NMR Behavior of the Latter