Ein Weg zu gemischten Pnictogenylboranen

Chain and ring [H PEH ] oligomers (E=B, Al; n=2-15) have been computationally studied at the B3LYP/def2-TZVP level of theory. A strong tendency to cyclization was found for the chain Al-P oligomers with n>7, whereas analogous long B-P oligomers can exist as chain structures. Subsequent oligomerization enthalpies approach each other very closely for the ring and chain oligomers with an increase of n. However, these oligomers have very different electronic properties with band gaps below 0.2 eV for the chain [H PBH ] and more than 5 eV for the ring isomer [H PEH ] . The molecular orbitals in the ring oligomers are highly delocalized, whereas for the chain isomers, the HOMO and LUMO are localized at the different ends of the oligomeric chain.

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Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Pomogaeva

Scheer

Timoshkin

2018

Chemistry A European J

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Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH₂ Groups (E=P, As)

Bauer

Seidl

et al. 2019

Chemistry A European J

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The pnictogenyl Group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac=HC[C(Me)N(Ar)]2, Ar: Dipp=2,6‐iPr2C6H3; M=Al, Ga, In; E=P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to monosubstituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E=P, M=Ga(1), In (2); E=As, M=Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1–4, the reactions of the corresponding halides with LiPH2⋅DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E=P, M=Al (5), Ga (6), In (7); E=As, M=Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5–9 are the first examples of monomeric Group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.

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NHC‐Stabilized Mixed Group 13/14/15 Element Hydrides

Ackermann,

Szlosek,

Riesinger

et al. 2024

Chemistry A European J

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The syntheses of novel N‐heterocyclic carbene (NHC) adducts of group 13, 14 and 15 element hydrides are reported. Salt metathesis reactions between NaPH2 and IDipp·GeH2BH2OTf (1) (IDipp = 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) led to mixtures of the two isomers IDipp·GeH2BH2PH2 (2a) and IDipp·BH2GeH2PH2 (2b); by altering the reaction conditions an almost exclusive formation of 2b was achieved. Attempts to purify mixtures of 2a and 2b by re‐crystallization from THF afforded a salt [IDipp·GeH2BH2·IDipp][PHGeH2BH2PH2BH2GeH2] (4) that contains the novel anionic cyclohexyl‐like inorganic heterocycle [PHGeH2BH2PH2BH2GeH2]‐. In addition, the borane adducts IDipp·GeH2BH2PH2BH3 (3a) and IDipp·BH2GeH2PH2BH3 (3b) as even longer chain compounds were obtained from reactions of 2a/2b with H3B·SMe2 and were studied by NMR spectroscopy. Accompanying DFT computations give insight into the mechanism and energetics associated with 2a/2b isomerization as well as their decomposition pathways.

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Ein Weg zu gemischten Pnictogenylboranen

Cited by 6 publications

References 78 publications

Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH₂ Groups (E=P, As)

NHC‐Stabilized Mixed Group 13/14/15 Element Hydrides

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Ein Weg zu gemischten Pnictogenylboranen

Cited by 6 publications

References 78 publications

Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)

Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)

Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 Groups (E=P, As)

NHC‐Stabilized Mixed Group 13/14/15 Element Hydrides

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Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H₂PEH₂]_n Oligomers (E=B, Al; n=1–15)

Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH₂ Groups (E=P, As)