Online citations, reference lists, and bibliographies.
← Back to Search

Aluminum(I)/Boron(III) Redox Reactions.

A. Hofmann, Conor Pranckevicius, Tobias Tröster, H. Braunschweig
Published 2019 · Chemistry, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy Visualize in Litmaps
Share
Reduce the time it takes to create your bibliography by a factor of 10 by using the world’s favourite reference manager
Time to take this seriously.
Get Citationsy
Reactions between BIII species and the novel nucleophilic cyclopentadienyl-stabilized AlI reagent (1) result in a diversity of complexes bearing different Al/B oxidation states and coordination geometries. With the triarylborane B(C6 F5 )3 , a simple AlI →BIII adduct is formed. In contrast, a bulky aryldihaloborane undergoes oxidative addition with the formation of a covalent bora-alane species. With an N-heterocyclic carbene-stabilized amino(bromo)borenium ion, a redox reaction was observed, where the product is a borylene-alane BI →AlIII complex. Additionally, reaction of 1 with BI3 results in complete scrambling of all of the Al/B-bound substituents, and the formation of a cyclopentadienylboron(I)→AlI3 complex. These latter reactions are the first examples of the reduction of a boron(III) compound to a borylene by a p-block reagent, and illustrate how subtle changes in the nature of the borane can result in highly divergent reaction outcomes.
This paper references
10.1002/ANIE.199105641
The Tetrameric Aluminum(I) Compound [{Al(η5‐C5Me5)}4]
Carsten Dohmeier (1991)
10.1002/ANGE.19911030527
Die tetramere Aluminium(I)‐Verbindung [{Al(η5‐C5Me5)}4]
Carsten Dohmeier (1991)
10.1002/ANIE.199317291
A Simple Synthesis of [(Cp*Al)4] and Its Conversion to the Heterocubanes [(Cp*AlSe)4] and [(Cp*AlTe)4] (Cp* = η5‐C5(CH3)5)
S. Schulz (1993)
10.1002/ANGE.19931051233
Eine einfache Synthese von [(Cp*Al)4] und dessen Umsetzung zu den Heterocubanen [(Cp*AlSe)4] und [(Cp*AlTe)4] (Cp* = η5‐C5(CH3)5)
S. Schulz (1993)
10.1002/ANGE.19941061731
Donorstabilisiertes Aluminium(I)‐bromid
M. Mocker (1994)
10.1002/ANGE.19941060926
Synthese und Struktur des ersten dimeren Iminoalans mit einem Al2N2-Heterocyclus†‡
S. Schulz (1994)
10.1002/ANIE.199409691
Synthesis and structure of the first dimeric iminoalane containing an Al2N2 heterocycle
S. Schulz (1994)
10.1002/ANIE.199424821
[(CpNi)2(Cp*Al)2]: Cp*Al as a Bridging Two-Electron Ligand†‡
Carsten Dohmeier (1995)
10.1002/ANGE.19961080805
Hauptgruppenelementanaloga von Carbenen, Olefinen und kleinen Ringen
M. Driess (1996)
10.1002/ANIE.199601291
Aluminum(I) and Gallium(I) Compounds: Syntheses, Structures, and Reactions
Carsten Dohmeier (1996)
10.1021/OM960375M
Pentabenzylcyclopentadienides of Lithium
Carsten Dohmeier (1996)
10.1002/ANIE.199608281
Main Group Element Analogues of Carbenes, Olefins, and Small Rings
M. Driess (1996)
10.1002/ANGE.19961080204
Aluminium(I)‐ und Gallium(I)‐ Verbindungen: Synthesen, Strukturen und Reaktionen
Carsten Dohmeier (1996)
10.1002/ANIE.199700701
[(η5‐C5Me5)AlFe(CO)4]—Synthesis, Structure, and Bonding
J. Weiss (1997)
10.1002/ANGE.19971090127
[(η5‐Cp*)AlFe(CO)4] – Synthese, Struktur, Bindungsverhältnisse
J. Weiss (1997)
10.1021/JA9806433
SYNTHESIS AND CHARACTERIZATION OF A TERMINAL BORYLENE (BORANEDIYL) COMPLEX
A. Cowley (1998)
10.1016/S0022-328X(98)00555-5
Cyclopentadienylderivate von Aluminium(I)
H. Sitzmann (1998)
10.1002/(SICI)1521-3773(19980803)37:13/14<1952::AID-ANIE1952>3.0.CO;2-U
The Behavior of [RAlX2⋅THF] Compounds under Reductive Conditions: Tetrakis[tris(trimethylsilyl)methylaluminum(I)]—A Neutral Aluminum(I) Compound with σ‐Bound Alkyl Groups and a Tetrahedral Structure
Christoph Schnitter (1998)
10.1002/(SICI)1521-3757(19980703)110:13/14<2059::AID-ANGE2059>3.0.CO;2-F
Das Verhalten von [RAlX2⋅THF]‐Verbindungen unter reduktiven Bedingungen: Tetrakis[tris(trimethylsilyl)methylaluminium(I)] – eine neutrale Aluminium(I)‐Verbindung mit σ‐gebundenen Alkylresten und tetraedrischer Struktur
Christoph Schnitter (1998)
10.1002/(SICI)1521-3773(19991004)38:19<2830::AID-ANIE2830>3.0.CO;2-E
Coordination Chemistry of Aluminum, Gallium, and Indium at Transition Metals.
Fischer (1999)
10.1021/JA992573L
A Theoretical Study of Free and Fe(CO)4-Complexed Borylenes (Boranediyls) and Heavier Congeners: The Nature of the Iron-Group 13 Element Bonding
C. Macdonald (1999)
10.1021/OM9906114
Reaction of Decamethylsilicocene with Group 13 Element Halides: Insertions, Rearrangements, and Eliminations
Udo Holtmann (1999)
10.1002/(SICI)1521-3757(19991004)111:19<3002::AID-ANGE3002>3.0.CO;2-B
Koordinationschemie von Aluminium, Gallium und Indium an Übergangsmetallen
Roland A. Fischer (1999)
10.1021/JA993537P
A Lewis Acid Adduct of an Alanediyl: An Aluminum(I)−Boron Donor−Acceptor Bond
J. D. Gorden (2000)
10.1002/1521-3773(20001215)39:24<4531::AID-ANIE4531>3.0.CO;2-K
[HC{(CMe)(NAr)}2]Al[(NSiMe3)2N2] (Ar=2,6-iPr2C6H3): The First Five-Membered AlN4 Ring System
Chunming Cui (2000)
10.1021/OM990936K
Nature of the Chemical Bond between a Transition Metal and a Group-13 Element: Structure and Bonding of Transition Metal Complexes with Terminal Group-13 Diyl Ligands ER (E = B to Tl; R = Cp, N(SiH3)2, Ph, Me)
J. Uddin (2000)
10.1002/1521-3773(20001201)39:23<4274::AID-ANIE4274>3.0.CO;2-K
Synthesis and Structure of a Monomeric Aluminum(I) Compound [{HC(CMeNAr)2 }Al] (Ar=2,6-iPr2 C6 H3 ): A Stable Aluminum Analogue of a Carbene.
Chunming Cui (2000)
10.1002/1099-0682(200009)2000:9<1927::AID-EJIC1927>3.0.CO;2-K
Borane-stabilized Boranediyls (Borylenes): Neutral nido-1-Borane-2,3,4,5,6-pentamethyl-2,3,4,5,6-pentacarbahexaboranes(6)
P. Greiwe (2000)
10.1039/B007341P
A valence isomer of a dialane
J. D. Gorden (2001)
10.1021/JA003185I
Facile synthesis of cyclopropene analogues of aluminum and an aluminum pinacolate, and the reactivity of LAl[eta(2)-C(2)(SiMe(3))(2)] toward unsaturated molecules (L=HC[(CMe)(NAr)](2), Ar=2,6-i-Pr(2)C(6)H(3)).
Chunming Cui (2001)
10.1002/1521-3773(20010601)40:11<2172::AID-ANIE2172>3.0.CO;2-Y
Stable, Monomeric Imides of Aluminum and Gallium: Synthesis and Characterization of [{HC(MeCDippN)2 }MN-2,6-Trip2 C6 H3 ] (M=Al or Ga; Dipp=2,6-iPr2 C6 H3 ; Trip=2,4,6-iPr3 C6 H2 ).
N. Hardman (2001)
10.1021/JA0201754
Low-Valent Group-13 Chemistry. Theoretical Investigation of the Structures and Relative Stabilities of Donor−Acceptor Complexes R3E−E‘R‘ and Their Isomers R2E−E‘RR‘ †
A. Timoshkin (2002)
10.1021/OM0209935
η1 versus η5 Bonding Modes in Cp*Al(I) Adducts of 9-Borafluorenes
P. Romero (2003)
10.1002/EJIC.200400159
Reactions of the Aluminum(I) Monomer LAl [L = HC{(CMe)(NAr)}2; Ar = 2,6‐iPr2C6H3] with Imidazol‐2‐ylidene and Diphenyldiazomethane. A Hydrogen Transfer from the L Ligand to the Central Aluminum Atom and Formation of the Diiminylaluminum Compound LAl(N=CPh2)2
H. Zhu (2004)
10.1002/ANGE.200353114
AlCp* als Steuerligand: C‐H‐ und Si‐H‐Bindungsaktivierung am reaktiven Intermediat [Ni(AlCp*)3]
T. Steinke (2004)
10.1002/ANIE.200353114
AlCp* as a directing ligand: C--H and Si--H bond activation at the reactive intermediate [Ni(AlCp*)(3)].
T. Steinke (2004)
10.1002/ANIE.200353406
[[HC(CMeNAr)(2)](2)Al(2)P(4)] (Ar=2,6-iPr(2)C(6)H(3)): a reduction to a formal [P(4)](4-) charged species.
Y. Peng (2004)
10.1021/JA0475712
Two types of intramolecular addition of an Al-N multiple-bonded monomer LAlNAr' arising from the reaction of LAl with N3Ar' (L = HC[(CMe)(NAr)]2, Ar' = 2,6-Ar2C6H3, Ar = 2,6-iPr2C6H3).
H. Zhu (2004)
10.1002/ANIE.200461209
[LAl(mu-S3)2AlL]: a homobimetallic derivative of the sulfur crown S8.
Y. Peng (2004)
10.1002/EJIC.200400922
A Rearrangement of Azobenzene upon Interaction with an Aluminum(I) Monomer LAl {L = HC[(CMe)(NAr)]2, Ar = 2,6‐iPr2C6H3}
H. Zhu (2005)
10.1002/ZAAC.200500129
Synthesis and Characterization of the Novel AlI Compound Al(C5Me4Ph): Comparison of the Coordination Chemistry of Al(C5Me5) and Al(C5Me4Ph) at d10 Metal Centers1)
Beatrice Buchin (2005)
10.1021/OM050698V
Syntheses and Structural Characterization of a LAl(N3)N[μ-Si(N3)(tBu)]2NAl(N3)L and a Monomeric Aluminum Hydride Amide LAlH(NHAr) (L = HC[(CMe)(NAr)]2, Ar = 2,6-iPr2C6H3)
H. Zhu (2005)
10.1002/ANIE.200500899
A stable aluminacyclopropene LAl(eta2-C2H2) and its end-on azide insertion to an aluminaazacyclobutene.
H. Zhu (2005)
10.1039/B505307B
Chemistry of aluminium(I).
H. Roesky (2005)
10.1021/JA052400Y
The selective preparation of an aluminum oxide and its isomeric C-H-activated hydroxide.
H. Zhu (2005)
10.1021/JA064035W
Synthesis of an aluminum spirocyclic hybrid with an inorganic B2O3 and an organic C3N2 core.
Z. Yang (2006)
10.1021/JA057731P
Aluminacyclopropene: syntheses, characterization, and reactivity toward terminal alkynes.
H. Zhu (2006)
10.1039/B518065A
The Al(I) bisimidinate Al(DDP) as a metalloid NHC type ligand for Pd(0) complexes and clusters.
Andreas Kempter (2006)
10.1002/ANIE.200600423
Al-Eu and Al-Yb donor-acceptor bonds.
M. Gamer (2006)
10.1002/ANGE.200600423
Al‐Eu‐ und Al‐Yb‐Donor‐Acceptor‐Bindungen
M. Gamer (2006)
10.1039/B609475A
A single-bonded cationic terminal borylene complex.
D. Vidović (2006)
10.1002/CHEM.200601096
Pt(0) and Pd(0) olefin complexes of the metalloid N-heterocyclic carbene analogues [E(I)(ddp)] (ddp=2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)imino}-2-pentene; E=Al, Ga): ligand substitution, H--H and Si--H bond activation, and cluster formation.
Andreas Kempter (2007)
10.1016/J.ICA.2007.04.009
Al4(C5Me4H)4: Structure, reactivity and bonding
M. Huber (2008)
10.1039/b816377d
Compounds with low-valent group 13 metals as ligands for electron poor main group and transition metals.
P. Roesky (2009)
10.1002/ANGE.201200954
Organoaluminium‐Boryl‐Komplexe
Nicole Dettenrieder (2012)
10.1002/anie.201200954
Organoaluminum boryl complexes.
Nicole Dettenrieder (2012)
10.1002/EJIC.201300317
From AlCp*‐ and GaCp*‐Ligated Ruthenium Hydrides to Zinc‐Rich Heterometallic Complexes
M. Molon (2013)
10.1039/c3cs35510a
Transition metal borylene complexes.
H. Braunschweig (2013)
10.1002/anie.201408371
Synthesis and reactivity of a CAAC-aminoborylene adduct: a hetero-allene or an organoboron isoelectronic with singlet carbenes.
Fatme Dahcheh (2014)
10.1002/anie.201406304
Temperature-dependent electron shuffle in molecular Group 13/15 intermetallic complexes.
C. Ganesamoorthy (2014)
10.1021/OM401163A
Half-Sandwich Rare-Earth-Metal Alkylaluminate Complexes Bearing Peripheral Boryl Ligands
Nicole Dettenrieder (2014)
10.1039/c4dt02155j
Reactivity of boryllithium with AlMe3, AlEt3, and GaMe3, including the synthesis of a lanthanum heterogallate complex.
Nicole Dettenrieder (2014)
10.1021/ja5038337
Oxidative addition of σ bonds to an Al(I) center.
Terry Chu (2014)
10.1016/J.JORGANCHEM.2013.08.039
Group-13 carbenoid ligands at tungsten: Coordination and C–H activation
M. Molon (2014)
10.1039/c4cc05028b
Sequential Bi-C bond activation reactions of BiEt₃ via insertion reactions of RE {R = HC[C(Me)N(2,6-i-Pr₂C₆H₃)]₂; E = Al, Ga, In}.
C. Ganesamoorthy (2014)
10.1021/ACS.ORGANOMET.5B00793
Transition Metal-like Oxidative Addition of C–F and C–O Bonds to an Aluminum(I) Center
Terry Chu (2015)
10.1039/C6CC08449D
Boryl substituted group 13 metallylenes: complexes with an iron carbonyl fragment.
Deepak Dange (2016)
10.1002/chem.201504537
Serendipitous Observation of AlI Insertion into a C-O Bond in L2 PhB (L=Oxazol-2-ylidene).
Lingbing Kong (2016)
10.1021/acs.inorgchem.6b01668
Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center.
Terry Chu (2016)
10.1002/anie.201509289
Dative Bonding between Group 13 Elements Using a Boron-Centered Lewis Base.
H. Braunschweig (2016)
10.1002/anie.201607735
Oxidative Cleavage of C=S and P=S Bonds at an AlI Center: Preparation of Terminally Bound Aluminum Sulfides.
Terry Chu (2016)
10.1021/ACS.INORGCHEM.6B01488
Oxidative Addition of π-Bonds and σ-Bonds to an Al(I) Center: The Second-Order Carbene Property of the AlNacNac Compound.
W. Schoeller (2016)
10.1021/acs.inorgchem.6b00462
Completing the Heterocubane Family [Cp*AlE]4 (E = O, S, Se, and Te) by Selective Oxygenation and Sulfuration of [Cp*Al]4: Density Functional Theory Calculations of [Cp*AlE]4 and Reactivity of [Cp*AlO]4 toward Hydrolysis.
Adrian C. Stelzer (2016)
10.1002/ANGE.201509289
Dative Wechselwirkungen einer Bor‐zentrierten Lewis‐Base mit Gruppe‐13‐Elementen
H. Braunschweig (2016)
10.1039/c6dt01154c
Insight into the reaction mechanisms for oxidative addition of strong σ bonds to an Al(i) center.
Xiangfei Zhang (2016)
10.1007/s00894-017-3539-x
Stability and donor-acceptor bond in dinuclear organometallics CpM1–M2Cl3 (M1, M2 = B, Al, Ga, In; Cp = η5–C5H5)
Yaru Dang (2017)
10.1002/anie.201705153
Borylenes: An Emerging Class of Compounds.
M. Soleilhavoup (2017)
10.1002/ANGE.201705153
Borylene: eine aufstrebende Verbindungsklasse
M. Soleilhavoup (2017)
10.1021/acs.inorgchem.7b00716
Unusual Reactions of NacNacAl with Urea and Phosphine Oxides.
Terry Chu (2017)
10.1021/acs.inorgchem.6b03127
Diverse Reactivity of ECp* (E = Al, Ga) toward Low-Coordinate Transition Metal Amides [TM(N(SiMe3)2)2] (TM = Fe, Co, Zn): Insertion, Cp* Transfer, and Orthometalation.
Jana Weßing (2017)
10.1021/acs.inorgchem.6b02993
Formation of Boron-Main-Group Element Bonds by Reactions with a Tricoordinate Organoboron L2PhB: (L = Oxazol-2-ylidene).
Lingbing Kong (2017)
10.1002/ANGE.201610072
Synthese und Reaktivität von Verbindungen mit elektronenpräzisen B‐B‐Einfach‐ und B‐B‐Mehrfachbindungen
Merle Arrowsmith (2017)
10.1002/anie.201708496
Electronic Delocalization in Two and Three Dimensions: Differential Aggregation in Indium "Metalloid" Clusters.
A. Protchenko (2017)
10.1021/acs.jpca.7b02075
The Role of Ligand Steric Bulk in New Monovalent Aluminum Compounds.
Warren W Tomlinson (2017)
10.1039/c7cc00325k
An open route to asymmetric substituted Al-Al bonds using Al(i)- and Al(iii)-precursors.
B. Li (2017)
10.1002/anie.201610072
Formation and Reactivity of Electron-Precise B-B Single and Multiple Bonds.
Merle Arrowsmith (2017)
10.1021/jacs.7b08890
A Stable Neutral Compound with an Aluminum-Aluminum Double Bond.
P. Bag (2017)
10.1021/jacs.7b04841
Oxidative Cleavage of the C═N Bond on Al(I).
Terry Chu (2017)
10.1002/chem.201705233
A General Route to Metal-Substituted Dipnictenes of the Type [L(X)M]2 E2.
Lars Tuscher (2018)
10.1038/s41586-018-0037-y
Synthesis, structure and reaction chemistry of a nucleophilic aluminyl anion
Jamie Hicks (2018)
10.1002/anie.201802321
Reactions of Fluoroalkenes with an Aluminium(I) Complex.
Clare Bakewell (2018)
10.1126/science.aaq1684
Nitrogen fixation and reduction at boron
Marc-André Légaré (2018)
10.1002/chem.201802300
Lewis-Base-Induced Disproportionation of a Dialane.
A. Hofmann (2018)
10.1002/EJIC.201701347
A Route to Aluminumdiisocyanate and ‐diisothiocyanate from an Al(I) Precursor
Soumen Sinhababu (2018)
10.1021/jacs.8b05398
Complexation and Release of N-Heterocyclic Carbene-Aminoborylene Ligands from Group VI and VIII Metals.
Conor Pranckevicius (2018)



This paper is referenced by
10.1002/EJIC.202100224
Amino−Organolithium Compounds and their Aggregation for the Synthesis of Amino−Organoaluminium Compounds
A. Bodach (2021)
10.1007/s00214-021-02801-5
Chemistry of group-10 metals monohaloalumylene complexes [TM(CO)3AlX]: a DFT study
A. Sekar (2021)
10.1021/acs.inorgchem.9b03701
Reactions of an Aluminum(I) Reagent with 1,2-, 1,3-, and 1,5-Dienes: Dearomatization, Reversibility, and a Pericyclic Mechanism.
Clare Bakewell (2020)
10.1002/anie.202009644
Planar Cyclopenten‐4‐yl Cations: Highly Delocalized π Aromatics Stabilized by Hyperconjugation
Samuel Nees (2020)
10.1039/d0sc02686g
Recent advances in low oxidation state aluminium chemistry
Katie Hobson (2020)
10.1016/j.ccr.2020.213647
Boron-heteroelement (B–E; E = Al, C, Si, Ge, N, P, As, Bi, O, S, Se, Te) multiply bonded compounds: Recent advances
R. Borthakur (2020)
10.1002/nadc.20204093482
Trendbericht Anorganische Chemie: Hauptgruppen
Christian Hering‐Junghans (2020)
10.1002/anie.202007530
The Aluminyl Anion: A New Generation of Aluminium Nucleophile.
Jamie Hicks (2020)
10.1002/chem.202002932
Stack by Stack: From the Free Cyclopentadienylgermanium Cation Via Heterobimetallic Main‐Group Sandwiches to Main‐Group Sandwich Coordination Polymers
Marcel Schorpp (2020)
10.1002/ANGE.202009644
Stabilisierung planarer Cyclopenten‐4‐yl‐Kationen durch Hyperkonjugation und π‐Delokalisierung
Samuel Nees (2020)
10.1039/c9dt04763h
The unique β-diketiminate ligand in aluminum(i) and gallium(i) chemistry.
M. Zhong (2020)
10.1002/anie.201902655
Heterodiatomic Multiple Bonding in Group 13: A Complex with a Boron-Aluminum π Bond Reduces CO2.
A. Hofmann (2019)
10.1002/ange.201907749
Ein neutraler “Aluminocen”‐Sandwich‐Komplex: η1‐ vs. η5‐Koordination eines Pentaarylborols mit ECp* (E=Al, Ga; Cp*=C5Me5)
Christian P Sindlinger (2019)
10.1002/anie.201907749
A Neutral “Aluminocene” Sandwich Complex: η1‐ versus η5‐Coordination Modes of a Pentaarylborole with ECp* (E=Al, Ga; Cp*=C5Me5)
Christian P Sindlinger (2019)
Semantic Scholar Logo Some data provided by SemanticScholar