Synthesis and crystal structure of dinuclear [(thf)3YCl2{μ-P(H)C6H2-2,4,6-Me3}]2 with seven-coordinate yttrium atoms

Krieck, Sven; Görls, Helmar; Westerhausen, Matthias

doi:10.1016/j.inoche.2009.02.026

Cited by 11 publications

(5 citation statements)

References 20 publications

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“…This also prevents us from observing or extracting any meaningful 1 J P–H coupling constants from the 31 P NMR spectrum of the complex (Figure S34). However, the 1 J P–H coupling constant can be extracted from the 1 H NMR spectrum of 5 (Figure S33), showing the typical PH doublet between 5.16 and 4.61 ppm with a 1 J P–H coupling constant of 221 Hz, which is consistent with other mesityl phosphanido complexes throughout the literature. − To the best of our knowledge, complex 5 is the first example of an anionic primary phosphanido ligand bound to niobium(V) reported in the literature so far. The only related report we were able to find, was the coordination of a series of neutral primary phosphine complexes with the general formula [NbCpCl 4 (PH 2 R)] (R = Mes, Ph, Cy, Ad, t Bu) reported by Hey-Hawkins .…”

Section: Resultssupporting

confidence: 79%

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

et al. 2022

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We report the facile synthesis of a rare niobium(V) imido NHC complex with a dianionic OCO-pincer benzimidazolylidene ligand (L 1 ) with the general formula [NbL 1 (N t Bu)PyCl] 1-Py. We achieved this by in situ deprotonation of the corresponding azolium salt [H 3 L 1 ][Cl] and subsequent reaction with [Nb(N t Bu)Py 2 Cl 3 ]. The pyridine ligand in 1-Py can be removed by the addition of B(C 6 F 5 ) 3 as a strong Lewis acid leading to the formation of the pyridine-free complex 1. In contrast to similar vanadium(V) complexes, complex 1-Py was found to be a good precursor for various salt metathesis reactions, yielding a series of chalcogenido and pnictogenido complexes with the general formula [NbL 1 (N t Bu)Py(EMes)] (E = O (2), S (3), NH (4), and PH (5)). Furthermore, complex 1-Py can be converted to alkyl complex (6) with 1 equiv of neosilyl lithium as a transmetallation agent. Addition of a second equivalent yields a new trianionic supporting ligand on the niobium center (7) in which the benzimidazolylidene ligand is alkylated at the former carbene carbon atom. The latter is an interesting chemically "noninnocent" feature of the benzimidazolylidene ligand potentially useful in catalysis and atom transfer reactions. Addition of mesityl lithium to 1-Py gives the pyridine-free aryl complex 8, which is stable toward "overarylation" by an additional equivalent of mesityl lithium. Electrochemical investigation revealed that complexes 1-Py and 1 are inert toward reduction in dichloromethane but show two irreversible reduction processes in tetrahydrofuran as a solvent. However, using standard reduction agents, e.g., KC 8 , K-mirror, and Na/Napht, no reduced products could be isolated. All complexes have been thoroughly studied by various techniques, including 1 H-, 13 C{ 1 H}-, and 1 H-15 N HMBC NMR spectroscopy, IR spectroscopy, and X-ray diffraction analysis.

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Section: Resultssupporting

confidence: 79%

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

et al. 2022

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“…For example, the 31 P NMR spectrum of 2 reveals two signals at d = 347.4 and 154.7 ppm, which are dramatically downfield from that observed for 1 (d = À62.5 ppm) and other reported yttrium phosphido compounds: [Y{P(SiMe 3 ) 2 } 3 ] 2 (d = À107.8 ppm), [14] [Cp* 2 Y{P(H)Ph}] 2 (d = À107 ppm) [15] and [Y{P(H)C 6 H 2 -2,4,6-Me 3 }Cl 2 (thf) 3 ] 2 (d = À18.9 ppm). [16] The signal at d = 154.7 ppm is comparable to that reported for the bridging phosphinidene unit in a lutetium phosphinidene [{2-(R 2 P)C 6 H 4 } 2 NLu(m-PMes)] 2 (d = 186.7 ppm). [11] Moreover, in the 1 H NMR spectrum, the signals for the -SiMe 3 group of the [P(SiMe 3 )C 6 H 3 -(2,6-iPr 2 )] À ligand and for the -PH group of the [P(H)C 6 H 3 -(2,6-iPr 2 )] À ligand were not observed.…”

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confidence: 65%

Well‐Defined Soluble P³⁻‐Containing Rare‐Earth‐Metal Compounds

Chen

et al. 2011

Angew Chem Int Ed

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“…This dianion coordinates to two Sc centers in a μ:η 2 -N,C η 2 -C,P-fashion. The Sc2–N7 bond length (2.057 (2) Å) falls in the range of 2.00–2.07 Å observed for Sc–N bonds in the Sc anilido complexes, , and the Sc1–P1 bond length (2.524 (1) Å) is close to the Ln–P bond lengths in the rare-earth metal–phosphido complexes if the difference in metal ion radii is counted . The Sc1–C67 bond is longer than the Sc2–C67 bond, 2.524 (2) vs 2.406 (2) Å, and both are significantly longer than those in the Sc alkyl complexes (2.19–2.31 Å) .…”

Section: Resultsmentioning

confidence: 82%

Versatile Reactivity of a Four-Coordinate Scandium Phosphinidene Complex: Reduction, Addition, and CO Activation Reactions

Kefalidis

Zhou

et al. 2013

J. Am. Chem. Soc.

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The four-coordinate scandium phosphinidene complex, [LSc(μ-PAr)]2 (L = (MeC(NDIPP)CHC(Me)(NCH2CH2N((i)Pr)2)), DIPP = 2,6-((i)Pr)2C6H3; Ar = 2,6-Me2C6H3) (1), has been synthesized in good yield, and its reactivity has been investigated. Although 1 has a bis(μ-phosphinidene)discandium structural unit, this coordinatively unsaturated complex shows high and versatile reactivity toward a variety of substrates. First, two-electron reduction occurs when substrates as 2,2'-bipyridine, elemental selenium, elemental tellurium, Me3P═S, or Ph3P═E (E = S, Se) is used, resulting in the oxidative coupling of two phosphinidene ligands 2[PAr](2-) into a diphosphene ligand [ArP-PAr](2-). Complex 1 easily undergoes nucleophilic addition reactions with unsaturated substrates, such as benzylallene, benzonitrile, tert-butyl isocyanide, and CS2. This complex also shows a peculiar reactivity to CO and Mo(CO)6, that includes C-P bond formation, C-C coupling and C-O bond cleavage of CO, to afford novel phosphorus-containing products. In the last two types of reactivity, reaction profiles have been computed (for the insertion of (t)BuNC and the CO activation by 1) at the DFT level. The unexpected/surprising sequence of steps in the latter case is also revealed.

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Synthesis and crystal structure of dinuclear [(thf)3YCl2{μ-P(H)C6H2-2,4,6-Me3}]2 with seven-coordinate yttrium atoms

Cited by 11 publications

References 20 publications

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

Well‐Defined Soluble P³⁻‐Containing Rare‐Earth‐Metal Compounds

Versatile Reactivity of a Four-Coordinate Scandium Phosphinidene Complex: Reduction, Addition, and CO Activation Reactions

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Synthesis and crystal structure of dinuclear [(thf)3YCl2{μ-P(H)C6H2-2,4,6-Me3}]2 with seven-coordinate yttrium atoms

Cited by 11 publications

References 20 publications

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

Reactivity and Structure of a Bis-phenolate Niobium NHC Complex

Well‐Defined Soluble P3−‐Containing Rare‐Earth‐Metal Compounds

Versatile Reactivity of a Four-Coordinate Scandium Phosphinidene Complex: Reduction, Addition, and CO Activation Reactions

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Well‐Defined Soluble P³⁻‐Containing Rare‐Earth‐Metal Compounds