Control of the Stereochemical Impact of the Lone Pair in Lead(II) Tris(pyrazolyl)methane Complexes. Improved Preparation of Na{B[3,5-(CF3)2C6H3]4}

Reger, Daniel L.; Wright, Terri D.; Little, Christine A.; Lamba, Jaydeep J. S.; Smith, Mark D.

doi:10.1021/ic0100121

Cited by 149 publications

(98 citation statements)

References 20 publications

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“…Electrochemical measurements were performed by using solutions in dichloromethane that contained 0.1 m [nBu 4 N]A C H T U N G T R E N N U N G [PF 6 ] as the electrolyte, a silver working electrode and a standard Calomel reference electrode. Chemicals were either obtained commercially or were prepared according to literature procedures (H 2 A C H T U N G T R E N N U N G (ttp), [26] H 2 -A C H T U N G T R E N N U N G (TpClpp), [26] [Li 2 A C H T U N G T R E N N U N G (ttp)], [27,28] B 2 Cl 4 , [10,11] magnesium anthracenide, [20,21] Na-A C H T U N G T R E N N U N G {[3,5-A C H T U N G T R E N N U N G (CF 3 ) 2 C 6 H 3 ] 4 B} [19] ).…”

Section: Methodsmentioning

confidence: 99%

“…Whereas the reactions of 5 a with either TlPF 6 in toluene or NaBPh 4 in CH 2 Cl 2 at ambient temperatures were unsuccessful, the addition of two equivalents of NaBA C H T U N G T R E N N U N G (Ar F ) 4 (Ar F : 3,5-C 6 H 3 A C H T U N G T R E N N U N G (CF 3 ) 2 ) [19] in CH 2 Cl 2 resulted in the precipitation of NaCl from the reaction medium and the formation of the extremely air-and moisture-sensitive salt [ 4 ] 2 (13 a, Scheme 5a).…”

Section: Wwwchemeurjorgmentioning

confidence: 99%

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Diboryl and Diboranyl Porphyrin Complexes: Synthesis, Structural Motifs, and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

Weiss

Hodgson

Boyd

et al. 2007

Chemistry A European J

100

123

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The syntheses of diboryl porphyrin complexes [(BX2)2(ttp)] (ttp: dianion of tetra-p-tolylporphyrin) and the B-B single-bond diboranyl complexes [(BX)2(ttp)] (X=F, Cl, Br, I) are given. The former are prepared from the reactions of BX3 (X=F, Cl) with [Li2(ttp)] and the latter from B(2)Cl(4) (X=Cl), the reaction of SbF3 with [(BCl)2(ttp)] (for X=F), and, in the cases of X=Br or I, in a remarkable reductive coupling reaction resulting directly from the reaction of BBr3 or BI3 with [Li2(ttp)]. Density functional theory (DFT) calculations on the thermochemical parameters for the reductive coupling reactions (and those calculated for related dipyrromethene complexes) indicate that a combination of the reducing ability of bromide and iodide ions combined with the constrained environment of the porphyrin ligand contribute to the driving force. The reductive coupling is also observed in the reaction of [(BCl2)2(ttp)] with nBuLi to give [(BnBu)2(ttp)], which was characterised crystallographically. The reaction of [(BCl)2(ttp)] with catechol gives a boron catecholato porphyrin complex, [B2(O(2)C(6)H(4))(ttp)]. Chloride abstraction from [(BCl)2(ttp)] gives the planar dication [B2(ttp)]2+, whereas chemical reduction of [(BCl)2(ttp)] by using magnesium anthracenide gives a neutral complex, [B(2)(ttp)], in which the TTP ligand has been reduced by two electrons to give an unusual example of an isophlorin complex. The cationic and neutral complexes [B2(ttp)]2+ and [B2(ttp)] were characterised through a combination of spectroscopic data that is supported by DFT calculations on the porphine analogues.

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Section: Methodsmentioning

confidence: 99%

Section: Wwwchemeurjorgmentioning

confidence: 99%

Diboryl and Diboranyl Porphyrin Complexes: Synthesis, Structural Motifs, and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

Weiss

Hodgson

Boyd

et al. 2007

Chemistry A European J

100

123

View full text Add to dashboard Cite

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“…(DME)NiCl 2 and (DME)NiBr 2 (DME = dimethoxyethane) were synthesized as previously described [12] [14] were synthesized according to literature procedure. Ionic liquids, except chloroaluminates, were dried under vacuum (10 -2 mbar) at 50°C to remove traces of water before use.…”

Section: Methodsmentioning

confidence: 99%

Biphasic Ni-Catalyzed Ethylene Oligomerization in Ionic Liquids

Lecocq

Olivier‐Bourbigou

2007

Oil & Gas Science and Technology - Rev. IFP

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Résumé -Oligomérisation biphasique de l'éthylène catalysée par les complexes du nickel dans les liquides ioniques -Les complexes diimines du nickel activés par un aluminoxane dans les liquides ioniques chloroaluminates forment des systèmes très actifs d'oligomérisation ou de polymérisation de l'éthylène en fonction de l'encombrement du ligand diimine. Le Ni(0) peut également être activé par un acide de Brönsted dans différents liquides ioniques non chloroaluminates. La nature du liquide ionique ainsi que la présence d'un ligand azoté ou non modifient considérablement les performances catalytiques de ces systèmes. Les produits oléfiniques de la réaction sont très faiblement solubles dans les liquides ioniques et peuvent être séparés par décantation. Le liquide ionique contenant le nickel peut être recyclé. Abstract -Biphasic Ni-Catalyzed Ethylene Oligomerization in Ionic Liquids

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“…2.59 ), [35] and bis(hydrotris(pyrazolyl)borato)lead(II) derivative [Pb{HB(3,5-Me 2 pz) 3 } 2 ] (av. 2.61 ).…”

mentioning

confidence: 99%

Molecular Nitrides with Titanium and Group 13–15 Elements

García-Castro¹,

Martı́n²,

Mena³

et al. 2009

Chemistry A European J

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Several heterometallic nitrido complexes were prepared by reaction of the imido-nitrido titanium complex [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) with amido derivatives of Group 13-15 elements. Treatment of 1 with bis(trimethylsilyl)amido [M{N(SiMe(3))(2)}(3)] derivatives of aluminum, gallium, or indium in toluene at 150-190 degrees C affords the single-cube amidoaluminum complex [{(Me(3)Si)(2)N}Al{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] (2) or the corner-shared double-cube compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Ga (3), In (4)]. Complexes 3 and 4 were also obtained by treatment of 1 with the trialkyl derivatives [M(CH(2)SiMe(3))(3)] (M = Ga, In) at high temperatures. The analogous reaction of 1 with [{Ga(NMe(2))(3)}(2)] at 110 degrees C leads to [{Ga(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (5), in which two [GaTi(3)N(4)] cube-type moieties are linked through a gallium-gallium bond. Complex 1 reacts with one equivalent of germanium, tin, or lead bis(trimethylsilyl)amido derivatives [M{N(SiMe(3))(2)}(2)] in toluene at room temperature to give cube-type complexes [M{(mu(3)-N)(2)(mu(3)-NH)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [M = Ge (6), Sn (7), Pb (8)]. Monitoring the reaction of 1 with [Sn{N(SiMe(3))(2)}(2)] and [Sn(C(5)H(5))(2)] by NMR spectroscopy allows the identification of intermediates [RSn{(mu(3)-N)(mu(3)-NH)(2)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] [R = N(SiMe(3))(2) (9), C(5)H(5) (10)] in the formation of 7. Addition of one equivalent of the metalloligand 1 to a solution of lead derivative 8 or the treatment of 1 with a half equivalent of [Pb{N(SiMe(3))(2)}(2)] afford the corner-shared double-cube compound [Pb(mu(3)-N)(2)(mu(3)-NH)(4){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] (11). Analogous antimony and bismuth derivatives [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}(2)] [M = Sb (12), Bi (13)] were obtained through the reaction of 1 with the tris(dimethylamido) reagents [M(NMe(2))(3)]. Treatment of 1 with [AlCl(2){N(SiMe(3))(2)}(OEt(2))] affords the precipitation of the singular aluminum-titanium square-pyramidal aggregate [{{(Me(3)Si)(2)N}Cl(3)Al(2)}(mu(3)-N)(mu(3)-NH)(2){Ti(3)(eta(5)-C(5)Me(5))(3)(mu-Cl)(mu(3)-N)}] (14). The X-ray crystal structures of 5, 11, 13, 14, and [AlCl{N(SiMe(3))(2)}(2)] were determined.

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Control of the Stereochemical Impact of the Lone Pair in Lead(II) Tris(pyrazolyl)methane Complexes. Improved Preparation of Na{B[3,5-(CF₃)₂C₆H₃]₄}

Cited by 149 publications

References 20 publications

Diboryl and Diboranyl Porphyrin Complexes: Synthesis, Structural Motifs, and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

Diboryl and Diboranyl Porphyrin Complexes: Synthesis, Structural Motifs, and Redox Chemistry: Diborenyl Porphyrin or Diboranyl Isophlorin?

Biphasic Ni-Catalyzed Ethylene Oligomerization in Ionic Liquids

Molecular Nitrides with Titanium and Group 13–15 Elements

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