Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center

Two equivalents of LGa (L=HC[C(Me)N(2,6-iPr C H )] ) reacted with PX (X=Cl, Br) with insertion into two P-X bonds and formation of [L(X)Ga] PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl occurred with twofold insertion and subsequent elimination of LGaCl and formation of the Ga-substituted diarsene [L(Cl)Ga] As (3). Analogous findings were observed in the reactions with Me NAsCl , yielding the unsymmetrically-substituted diarsene [L(Cl)Ga]As=As[Ga(NMe )L] (4). The reaction of As(NMe ) with LGa gave [L(Me N)Ga] As (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me N)Al] As (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt ) to give [L(Et N)Ga] Bi (7). Complexes 1-7 were characterized by NMR spectroscopy ( H, C, P), elemental analysis, and single-crystal X-ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.

Section: Introductionmentioning

confidence: 87%

A General Route to Metal‐Substituted Dipnictenes of the Type [L(X)M]₂E₂

Tuscher

Helling

Wölper

et al. 2018

“…[15] There have been previous computational studies that have investigated the energetics of s-a nd p-bond activation by the NacNacAl I complex through direct oxidative addition. [17,[20][21][22][23] However, this work is the first to shed light on the explicit role of the aromatic solvent molecule, and show how it is able to considerably enhancethe potency of the NacNacAl I system.…”

Section: Introductionmentioning

confidence: 93%

“…[12][13][14] This was employed recently by Nikonov and co-workerst oa ctivate the HÀH, HÀP, HÀN, HÀO, HÀSi, HÀB, and HÀC s bonds. [15] More recently,t he group of Nikonova lso showed that the NacNacAl I complex could activate even stronger s bonds, such as CÀF, CÀO, [16] PÀP, and CÀS, [17] and p bonds, such as C=Sa nd P=S. [18] It is believed that activation proceeds at as ingle group 13 metal center.…”

Section: Introductionmentioning

confidence: 99%

The Unusual Role of Aromatic Solvent in Single‐Site Aluminum^I Chemistry: Insights from Theory

Jain

Vanka

2017

The single-site activation of strong σ bonds (such as that of H-H, P-H, and N-H) remains a significant challenge in main-group chemistry, with only a few cases reported to date. In this regard, recent exciting experiments performed with aluminum complexes hold significance because they have been seen to activate a variety of strong σ bonds. Such chemistry is generally seen to occur in aromatic solvents. Current computational studies with DFT reveal the interesting reason for this: an explicit aromatic solvent molecule acts as a catalyst by converting the aluminum complex into aluminum during the process. Different cases of σ-bond activation by aluminum complexes have been investigated and the efficiency of H-X (X=H, NHtBu, PPh ) bond activation in the presence of an explicit benzene solvent molecule is orders of magnitude higher than that in its absence. The current work therefore reveals the chemistry of aluminum complexes to be richer and more complex than that previously realized, and shows it to be dependent on metal-solvent cooperativity; the first known example of its kind in main-group chemistry.

“…Crystal structure of species 11 (2,6-diispropylphenyl bulk and benzophenone scaffold are minimized, whereas hydrogen atomsa re omitted for clarity). Selectedbond lengths []a nd angles [8]: Al1ÀN1 1.876(2),A l1ÀN2 1.884(2), Al1ÀN3 1.842(2), Al1ÀO1 1.741(2), N3ÀC30 1.271(3),C30ÀC31 1.508(3), C30ÀC37 1.592(2), C37ÀO1 1.420(2);N 1-Al1-N2 97.73 (7), N3-Al1-O1 94.20 (7), C38-C37-C44 114.7(2), C31-C30-C37 121.9 (7).…”

Section: Scheme6preparation Of Compound 10mentioning

confidence: 99%

“…Activation of strong bonds by reduced main-group compounds has received significant attention [1] in the contexto f development of main-group surrogates for the common transition-metal-based catalysts. [2] In this context, NacNacAl (1, (NacNac = [ArNC(Me)CHC(Me)NAr] À ,A r= 2,6-iPr 2 C 6 H 3 ), [3] ad iketiminate-supported Group 13 carbenoid, [4] is noteworthy because of its well-documented propensityt oc leave strongH ÀX bonds, [5] CÀFa nd CÀOb onds, [6] EÀE( E = S, P) bonds, [7] and even the C=X( X= S, N) multiple bonds in thiourea andg uanidines. [8] With other multiple bonds, compound 1 showeda wealth of reactivity in coordination of alkynes [9] and alkenes [10] and in cyclizationw ith heterocumulenes.…”

Section: Introductionmentioning

confidence: 99%

Adduct of NacNacAl with Benzophenone and Its Coupling Chemistry

Dmitrienko

Britten

Spasyuk

et al. 2019

Self Cite

Reaction of NacNacAl (NacNac=[DippNC(Me)CHC(Me)NDipp]−) with one equivalent of benzophenone affords a ketylate species NacNacAl(η2(C,O)‐OCPh2) that undergoes easy cyclization reactions with unsaturated substrates. The scope of substrates included benzophenone, aldimine (PhNC(Ph)H), quinoline, phenyl nitrile, trimethylsilyl azide, and a saturated cyclic thiourea. The latter substrate reacted by an unusual C−N cleavage that left the C=S functionality intact. The new products were characterized by NMR spectroscopy and X‐ray diffraction analysis.