Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

Synthesis of four and five coordinated aluminum amidinate (PhC(NBu)2=L) compounds are reported herein along with their single-crystal X-ray structures and detailed characterizations using both, experimental and computational techniques. LAlCl2 (1) and L2AlCl (2) were synthesized by treating AlCl3 with PhC (NBu)2Li in an equivalent ratio of 1 : 1 and 1 :2, respectively. [LAl (C2H5)Cl] (3) was prepared from a reaction of AlCl2(C2H5) with PhC(NBu)2Li in an equivalent ratio of 1 :1. Reactivity of 3, an amidinate based organo-aluminum compound is explored for the various reactions. 3 produced [LAl(C2H5)(μ-F)]2 (4) on treatment with Me3SnF. Interestingly, [LAl(C2H5)Cl] (3) was converted to [LAlCl(μ-OEt)]2 (5) when refluxed in Et2O. 3 gives the monomeric and neutral cyclic (alkyl)(amino) carbene (cAAC) based radical [LAl(C2H5)(cAAC)] (6) on reduction with KC8 in the presence of cAAC.

[1]  D. Stalke,et al.  When Electrons Step in: Polarizing Effects Explored with Triisobutylaluminum. , 2021, Inorganic chemistry.

[2]  D. Stalke,et al.  Amidinate based indium(III) monohalides and β-diketiminate stabilized In(II)-In(II) bond: synthesis, crystal structure, and computational study. , 2020, Dalton transactions.

[3]  D. Stalke,et al.  Cyclic (Alkyl)(Amino)Carbene-Stabilized Aluminum and Gallium Radicals Based on Amidinate Scaffolds. , 2020, Inorganic chemistry.

[4]  S. Dutta,et al.  Cooperative Donor-Acceptor Interactions in Stabilizing Carbene-Borane and Carbene-Alane Compounds: A Theoretical Insight , 2020 .

[5]  K. Lyssenko,et al.  Calcium Amido Complexes Coordinated by Tridentate Amidinate Ligands: Synthesis, Structures and Catalytic Activity in Olefin Hydrophosphination and Polymerization of Cyclic Esters , 2019, European Journal of Inorganic Chemistry.

[6]  J. Brus,et al.  The addition of Grignard reagents to carbodiimides. The synthesis, structure and potential utilization of magnesium amidinates. , 2019, Dalton transactions.

[7]  D. Stalke,et al.  (PhC(NtBu)2Al)2(SiH2)4 six-membered heterocycle: comparable in structure to cyclohexane. , 2019, Chemical communications.

[8]  S. Dutta,et al.  Strengths of different Lewis bases in stabilizing titanium fluorides: A theoretical insight , 2019, Inorganica Chimica Acta.

[9]  Javier Martínez,et al.  Cyclic Carbonates from CO2 and Epoxides Catalyzed by Tetra- and Pentacoordinate Amidinate Aluminum Complexes , 2018, Organometallics.

[10]  D. Stalke,et al.  Silanylidene and Germanylidene Anions: Valence-Isoelectronic Species to the Well-Studied Phosphinidene. , 2018, Angewandte Chemie.

[11]  Javier Martínez,et al.  Amidinate Aluminium Complexes as Catalysts for Carbon Dioxide Fixation into Cyclic Carbonates , 2018 .

[12]  Yongxin Li,et al.  B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand. , 2018, Inorganic chemistry.

[13]  G. Deacon,et al.  Kinetic stabilisation of a molecular strontium hydride complex using an extremely bulky amidinate ligand. , 2018, Chemical communications.

[14]  S. Dutta,et al.  Synthesis and characterization of Lewis base stabilized mono- and di-organo aluminum radicals. , 2017, Chemical communications.

[15]  A. Wieck,et al.  New amidinate complexes of indium(iii): promising CVD precursors for transparent and conductive In2O3 thin films. , 2017, Dalton transactions.

[16]  G. Frenking,et al.  A Stable Neutral Radical in the Coordination Sphere of Aluminum. , 2017, Angewandte Chemie.

[17]  D. Stalke,et al.  Ein stabiles neutrales Radikal in der Koordinationssphäre des Aluminiums , 2017 .

[18]  Rui Liu,et al.  A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules. , 2016, Chemistry.

[19]  D. Stalke,et al.  An empirical correction for the influence of low‐energy contamination , 2015 .

[20]  D. Stalke,et al.  A stable dimer of SiS2 arranged between two carbene molecules. , 2015, Chemistry.

[21]  Dietmar Stalke,et al.  Comparison of silver and molybdenum microfocus X-ray sources for single-crystal structure determination , 2015, Journal of applied crystallography.

[22]  G. Sheldrick.  SHELXT – Integrated space-group and crystal-structure determination , 2015, Acta crystallographica. Section A, Foundations and advances.

[23]  G. Sheldrick.  Crystal structure refinement with SHELXL , 2015, Acta crystallographica. Section C, Structural chemistry.

[24]  D. Stalke,et al.  Facile Access to the Functionalized N-Donor Stabilized Silylenes PhC(NtBu)2SiX (X = PPh2, NPh2, NCy2, NiPr2, NMe2, N(SiMe3)2, OtBu) , 2012 .

[25]  D. Stalke,et al.  A début for base stabilized monoalkylsilylenes. , 2012, Chemical communications.

[26]  George M. Sheldrick,et al.  ShelXle: a Qt graphical user interface for SHELXL , 2011, Journal of applied crystallography.

[27]  P. Kongsaeree,et al.  Synthesis of high-molecular-weight poly(ε-caprolactone) catalyzed by highly active bis(amidinate) tin(II) complexes. , 2011, Dalton transactions.

[28]  M. Driess,et al.  N-heterocyclic carbene analogues with low-valent group 13 and group 14 elements: syntheses, structures, and reactivities of a new generation of multitalented ligands. , 2011, Chemical reviews.

[29]  Keyin Liu,et al.  Amidinate aluminium complexes: synthesis, characterization and ring-opening polymerization of rac-lactide. , 2010, Dalton transactions.

[30]  D. Stalke,et al.  High yield access to silylene RSiCl (R = PhC(NtBu)2) and its reactivity toward alkyne: synthesis of stable disilacyclobutene. , 2010, Journal of the American Chemical Society.

[31]  G. Sheldrick,et al.  A comparison of a microfocus X‐ray source and a conventional sealed tube for crystal structure determination , 2009 .

[32]  D. Stalke,et al.  Synthesis, characterization, and reaction of aluminum halide amides supported by a bulky beta-diketiminato ligand. , 2008, Inorganic chemistry.

[33]  D. A. Lemenovskii,et al.  Principal trends in the chemistry of amidinate complexes of main-group and transition elements , 2006 .

[34]  F. Weigend.  Accurate Coulomb-fitting basis sets for H to Rn. , 2006, Physical chemistry chemical physics : PCCP.

[35]  R. Herbst‐Irmer,et al.  Syntheses, characterization, and X-ray crystal structures of beta-diketiminate group 13 hydrides, chlorides, and fluorides. , 2006, Inorganic chemistry.

[36]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[37]  J. Platts,et al.  Synthesis, characterisation and theoretical studies of amidinato-indium(I) and thallium(I) complexes: isomers of neutral group 13 metal(I) carbene analogues. , 2005, Dalton transactions.

[38]  G. Yap,et al.  The insertion of carbodiimides into Al and Ga amido linkages. Guanidinates and mixed amido guanidinates of aluminum and gallium. , 2005, Inorganic chemistry.

[39]  R. Baker,et al.  Kinetic control over the thermal stability of the In-H bond: synthesis and characterization of amido indium hydride complexes. , 2004, Angewandte Chemie.

[40]  P. Hitchcock,et al.  A New Class of Linked-bis(N,N'-dialkylamidinate) Ligand: Applications in the Synthesis of Bimetallic Aluminium Complexes , 2002 .

[41]  F. Matthias Bickelhaupt,et al.  Chemistry with ADF , 2001, J. Comput. Chem..

[42]  H. Roesky,et al.  Synthesis and Structures of Mono(1-aza-allyl) Complexes of Aluminum† , 1999 .

[43]  Peter A. Schlüter,et al.  Bis(amidinate) Complexes of Silicon and Germanium , 1998 .

[44]  R. F. Jordan,et al.  Cationic Aluminum Alkyl Complexes Incorporating Amidinate Ligands. Transition-Metal-Free Ethylene Polymerization Catalysts , 1997 .

[45]  Holger Schwenk,et al.  Synthesis and Structures of Bis(tetramethylipiperidino)aluminum Halides-X-ray Crystal Structures of tmp2AlX (X = Cl, Br, I) and [tmp2A1(μ-F)l2 , 1997 .

[46]  Evert Jan Baerends,et al.  Relativistic regular two‐component Hamiltonians , 1993 .

[47]  U. Pieper,et al.  Sterische Cyclopentadienyl-Äquivalente in der Chemie der f-Elemente: Monomere, homoleptische Lanthanid(III)-tris[N,N′-bis(trimethylsilyl)-benzamidinate] , 1992 .

[48]  D. Stalke,et al.  Dimere Alkalimetallbenzamidinate: Einfluß des metallions auf die struktur , 1992 .

[49]  R. Bader,et al.  A quantum theory of molecular structure and its applications , 1991 .

[50]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[51]  L. Curtiss,et al.  Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint , 1988 .

[52]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[53]  A. Rauk,et al.  Carbon monoxide, carbon monosulfide, molecular nitrogen, phosphorus trifluoride, and methyl isocyanide as .sigma. donors and .pi. acceptors. A theoretical study by the Hartree-Fock-Slater transition-state method , 1979 .

[54]  Kazuo Kitaura,et al.  A new energy decomposition scheme for molecular interactions within the Hartree‐Fock approximation , 1976 .

[55]  Keiji Morokuma,et al.  Molecular Orbital Studies of Hydrogen Bonds. III. C=O···H–O Hydrogen Bond in H2CO···H2O and H2CO···2H2O , 1971 .

[56]  D. Stalke,et al.  An unprecedented 1,4-diphospha-2,3-disila butadiene (–PSi–SiP–) derivative and a 1,3-diphospha-2-silaallyl anion, each stabilized by the amidinate ligand , 2017 .

[57]  P. Hitchcock,et al.  Synthesis and structures of lithium, aluminium, gallium and lanthanide amidinates containing a γ-pendant amine functionality , 2000 .

[58]  I. Guzei,et al.  Synthesis and Structures of Cationic Aluminum and Gallium Amidinate Complexes , 2000 .

[59]  A. Rauk,et al.  On the calculation of bonding energies by the Hartree Fock Slater method , 1977 .

[60]  Kenneth B. Wiberg,et al.  Application of the pople-santry-segal CNDO method to the cyclopropylcarbinyl and cyclobutyl cation and to bicyclobutane , 1968 .