Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4] und [WO(N3)4⋅CH3CN]

As terically encumbering multidentate b-diketiminato ligand, tBu L2 ( tBu L2=[ArNC(tBu)CHC(tBu)NCH 2 CH 2 N(Me)-CH 2 CH 2 NMe 2 ] À ,A r = 2,6-iPr 2 C 6 H 3 ), is reported in this study along with its coordination chemistry to zirconium(IV). Using the lithio salt of this ligand,L i( tBu L2) (4), the zirconium(IV) precursor ( tBu L2)ZrCl 3 (6)c ould be readily prepared in 85 % yield ands tructurally characterized.R eduction of 6 with 2equiv of KC 8 resulted in formationo ft he terminal and mononuclear zirconium imide-chloride [C(tBu)CHC(t-Bu)NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ]Zr(=NAr)(Cl) (7)a st he result of reductive C=Nc leavage of the imino fragment in the multidentate ligand tBu L2 by an elusiveZ r II species( tBu L2)ZrCl (A). The azabutadienyl ligand in 7 can be further reduced by 2e À with KC 8 to afford the anionic imide [K(THF) 2 ]{[CH(tBu)CHC(tBu)NCH 2 CH 2 N(Me)CH 2 CH 2 N(Me)CH 2 ]-Zr=NAr} (8-2THF)i n4 2% isolated yield. Complex 8-2THF results from the oxidative addition of an amine CÀHb ond followed by migration to the vinylic group of the formal [C(tBu)CHC(tBu)NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ] À ligand in 7.A ll halidesi n6 can be replaced with azides to afford ( tBu L2)Zr(N 3 ) 3 (9)w hichw as structurally characterized, and reductionw ith two equiv of KC 8 also results in C=Nb ond cleavage of tBu L2 to form [C(tBu)CHC(tBu)NCH 2 CH 2 N-(Me)CH 2 CH 2 NMe 2 ]Zr(=NAr)(N 3 )( 10), instead of the expected azide disproportionation to N 3À and N 2 .S olid-state single crystal structural studies confirm the formation of mononuclear and terminal zirconium imido groups in 7, 8-Et 2 O,a nd 10 with Zr=NAr distances being 1.8776(10), 1.9505(15), and 1.881(3) ,r espectively.Scheme1.Multidentate ligands havingthe b-diketiminato motif,where Ar represents iPr 2 C 6 H 3 .[a] Dr.Scheme2.Synthetic entry to the lithio salt 4 of the b-diketiminato ligand tBu L2 starting from the trisamino precursor 1,which can be prepared by two separate reactionss temming from N,N,N'-trimethylethylenediamine.

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Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Kurogi

Chu

Chen

et al. 2019

Chemistry An Asian Journal

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Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2′‐Bipyridine Adducts

Deokar

Leitz

Stein

et al. 2016

Chemistry A European J

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The arsenic(III) and antimony(III) cyanides M(CN)3 (M=As, Sb) have been prepared in quantitative yields from the corresponding trifluorides through fluoride-cyanide exchange with Me3 SiCN in acetonitrile. When the reaction was carried out in the presence of one equivalent of 2,2'-bipyridine, the adducts [M(CN)3 ⋅(2,2'-bipy)] were obtained. The crystal structures of As(CN)3 , [As(CN)3 ⋅(2,2'-bipy)] and [Sb(CN)3 ⋅(2,2'-bipy)] were determined and are surprisingly different. As(CN)3 possesses a polymeric three-dimensional structure, [As(CN)3 ⋅(2,2'-bipy)] exhibits a two-dimensional sheet structure, and [Sb(CN)3 ⋅(2,2'-bipy)] has a chain structure, and none of the structures resembles those found for the corresponding arsenic and antimony triazides.

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The Uranium(VI) Oxoazides [UO₂(N₃)₂⋅CH₃CN], [(bipy)₂(UO₂)₂(N₃)₄], [(bipy)UO₂(N₃)₃]⁻, [UO₂(N₃)₄]²⁻, and [(UO₂)₂(N₃)₈]⁴⁻

Haiges

Vasiliu

Dixon

2016

Chemistry A European J

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The reaction between [UO F ] and an excess of Me SiN in acetonitrile solution results in fluoride-azide exchange and the uranium(VI) dioxodiazide adduct [UO (N ) ⋅CH CN] was isolated in quantitative yield. The subsequent reaction of [UO (N ) ⋅CH CN] with 2,2'-bipyridine (bipy) resulted in the formation of the azido-bridged binuclear complex [(bipy) (UO ) (N ) ]. The triazido anion [(bipy)UO (N ) ] was obtained by the reaction of [UO (N ) ⋅CH CN] with stoichiometric amounts of bipy and the ionic azide [PPh ][N ]. The reaction of [UO (N ) ] with two equivalents of the [PPh ][N ] resulted in the formation of the mononuclear tetraazido anion [UO (N ) ] as well as the azido-bridged binuclear anion [(UO ) (N ) ] . The novel uranium oxoazides were characterized by their vibrational spectra and in the case of [(bipy) (UO ) (N ) ]⋅CH CN, [PPh ][(bipy)UO (N ) ], [PPh ] [UO (N ) ], [PPh ] [UO (N ) ]⋅2CH CN, and [PPh ] [(UO ) (N ) ]⋅4CH CN by their X-ray crystal structures.

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Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N₃)₃], [MoO(N₃)₃⋅2 CH₃CN], [(bipy)MoO(N₃)₃], [MoO(N₃)₅]²⁻, [WO(N₃)₄] und [WO(N₃)₄⋅CH₃CN]

Cited by 5 publications

References 53 publications

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2′‐Bipyridine Adducts

The Uranium(VI) Oxoazides [UO₂(N₃)₂⋅CH₃CN], [(bipy)₂(UO₂)₂(N₃)₄], [(bipy)UO₂(N₃)₃]⁻, [UO₂(N₃)₄]²⁻, and [(UO₂)₂(N₃)₈]⁴⁻

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Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4] und [WO(N3)4⋅CH3CN]

Cited by 5 publications

References 53 publications

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2′‐Bipyridine Adducts

The Uranium(VI) Oxoazides [UO2(N3)2⋅CH3CN], [(bipy)2(UO2)2(N3)4], [(bipy)UO2(N3)3]−, [UO2(N3)4]2−, and [(UO2)2(N3)8]4−

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Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N₃)₃], [MoO(N₃)₃⋅2 CH₃CN], [(bipy)MoO(N₃)₃], [MoO(N₃)₅]²⁻, [WO(N₃)₄] und [WO(N₃)₄⋅CH₃CN]

The Uranium(VI) Oxoazides [UO₂(N₃)₂⋅CH₃CN], [(bipy)₂(UO₂)₂(N₃)₄], [(bipy)UO₂(N₃)₃]⁻, [UO₂(N₃)₄]²⁻, and [(UO₂)₂(N₃)₈]⁴⁻