Theoretical Studies on the Bonding Properties of Metal-metal Multiple Bond of Cp2M2(μ-B4N4H8)(M=V,Cr,Mn,Fe)†

doi:10.7503/cjcu20140327

Abstract

Abstract:

The geometry and bonding of metal-metal multiple bond complexes Cp₂M₂(μ-B₄N₄H₈)(M=V, Cr, Mn, Fe) were theoretically investigated and compared with Cp₂M₂(μ-C₈H₈). The calculated results show that in the ground states of Cp₂M₂(μ-B₄N₄H₈), the ligands B₄N₄H₈are all with B bridging atoms, the coordination numbers of M atom are all five. Among them, the structure and bonding of ground state of Cp₂M₂(μ-B₄N₄H₈)(M=V, Cr, Mn) are very close to Cp₂M₂(μ-C₈H₈); while the ground state of Cp₂Fe₂(μ-B₄N₄H₈) is different with Cp₂Fe₂(μ-C₈H₈) containing four-coordinated Fe. The ground-states of Cp₂M₂(μ-B₄N₄H₈)(M=V, Cr, Mn, Fe) are respectively triplet state with V-V triple bond, singlet state with Cr-Cr triple bond, triplet state with Mn-Mn double bond, and singlet state with Fe-Fe single bond.

Key words: Boron-nitrogen compound, Cyclooctatetraene(C8H8), Metal-metal multiple bond, Borazine(BnNn $H 2 n$ )

CLC Number:

O641

TrendMD:

LIU Nannan, DING Yihong. Theoretical Studies on the Bonding Properties of Metal-metal Multiple Bond of Cp₂M₂(μ-B₄N₄H₈)(M=V,Cr,Mn,Fe)^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1720.

Figures/Tables 4

References 29

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Complex	d^a(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^b(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^c(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^d(M-M)/ nm
Cp₂V₂(μ-B₄N₄H₈)-Iso1-singlet	0.228	0	0.218	0	0.227	0
Cp₂V₂(μ-B₄N₄H₈)-Iso1-triplet	0.245	-13.6	0.240	-73.0	0.244	-10.8
Cp₂V₂(μ-B₄N₄H₈)-Iso2-singlet	0.240	106.0	0.232	99.6	0.239	106.8
Cp₂V₂(μ-B₄N₄H₈)-Iso2-triplet	0.260	113.6	0.259	37.9	0.260	114.6
Cp₂V₂(μ-C₈H₈)-singlet^[26]	0.232	0	0.225	0	0.231	0
Cp₂V₂(μ-C₈H₈)-triplet^[26]	0.248	-6.3	0.245	-67.4	0.248	-6.3	0.244^[27]
Cp₂Cr₂(μ-B₄N₄H₈)-Iso1-singlet	0.229	0	0.224	0	0.228	0
Cp₂Cr₂(μ-B₄N₄H₈)-Iso1-triplet	0.245	22.3	0.259	-36.2	0.245	21.3
Cp₂Cr₂(μ-B₄N₄H₈)-Iso2-singlet	0.247	96.3	0.252	53.4	0.248	94.6
Cp₂Cr₂(μ-B₄N₄H₈)-Iso2-triplet	0.260	115.1	0.285	41.5	0.260	112.9
Cp₂Cr₂(μ-C₈H₈)-singlet^[26]	0.235	0	0.235	0	0.234	0	0.239^[28,29]
Cp₂Cr₂(μ-C₈H₈)-triplet^[26]	0.248	19.7	0.256	-33.8	0.248	19.7
Cp₂Mn₂(μ-B₄N₄H₈)-Iso1-singlet	0.266	0	0.258	0	0.262	0
Cp₂Mn₂(μ-B₄N₄H₈)-Iso1-triplet	0.262	-42.2	0.288	-38.4	0.262	-28.2
Cp₂Mn₂(μ-B₄N₄H₈)-Iso2-singlet	0.283	64.3	0.289	40.9	0.284	71.1
Cp₂Mn₂(μ-C₈H₈)-singlet	0.266	0	0.268	0	0.267	0
Cp₂Mn₂(μ-C₈H₈)-triplet	0.270	-12.1	0.265	5.1	0.267	-6.7
Cp₂Fe₂(μ-B₄N₄H₈)-Iso1-singlet	0.293	0	0.295	0	0.295	0
Cp₂Fe₂(μ-B₄N₄H₈)-Iso1-triplet	0.295	88.7	0.293	51.1	0.297	82.1
Cp₂Fe₂(μ-C₈H₈)-singlet	0.294	0	0.298	0	0.295	0
Cp₂Fe₂(μ-C₈H₈)-triplet	0.343	79.5	0.348	7.8	0.346	71.7

Complex	d^a(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^b(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^c(M-M)/ nm	ΔE/ (kJ·mol^-1)	d^d(M-M)/ nm
Cp₂V₂(μ-B₄N₄H₈)-Iso1-singlet	0.228	0	0.218	0	0.227	0
Cp₂V₂(μ-B₄N₄H₈)-Iso1-triplet	0.245	-13.6	0.240	-73.0	0.244	-10.8
Cp₂V₂(μ-B₄N₄H₈)-Iso2-singlet	0.240	106.0	0.232	99.6	0.239	106.8
Cp₂V₂(μ-B₄N₄H₈)-Iso2-triplet	0.260	113.6	0.259	37.9	0.260	114.6
Cp₂V₂(μ-C₈H₈)-singlet^[26]	0.232	0	0.225	0	0.231	0
Cp₂V₂(μ-C₈H₈)-triplet^[26]	0.248	-6.3	0.245	-67.4	0.248	-6.3	0.244^[27]
Cp₂Cr₂(μ-B₄N₄H₈)-Iso1-singlet	0.229	0	0.224	0	0.228	0
Cp₂Cr₂(μ-B₄N₄H₈)-Iso1-triplet	0.245	22.3	0.259	-36.2	0.245	21.3
Cp₂Cr₂(μ-B₄N₄H₈)-Iso2-singlet	0.247	96.3	0.252	53.4	0.248	94.6
Cp₂Cr₂(μ-B₄N₄H₈)-Iso2-triplet	0.260	115.1	0.285	41.5	0.260	112.9
Cp₂Cr₂(μ-C₈H₈)-singlet^[26]	0.235	0	0.235	0	0.234	0	0.239^[28,29]
Cp₂Cr₂(μ-C₈H₈)-triplet^[26]	0.248	19.7	0.256	-33.8	0.248	19.7
Cp₂Mn₂(μ-B₄N₄H₈)-Iso1-singlet	0.266	0	0.258	0	0.262	0
Cp₂Mn₂(μ-B₄N₄H₈)-Iso1-triplet	0.262	-42.2	0.288	-38.4	0.262	-28.2
Cp₂Mn₂(μ-B₄N₄H₈)-Iso2-singlet	0.283	64.3	0.289	40.9	0.284	71.1
Cp₂Mn₂(μ-C₈H₈)-singlet	0.266	0	0.268	0	0.267	0
Cp₂Mn₂(μ-C₈H₈)-triplet	0.270	-12.1	0.265	5.1	0.267	-6.7
Cp₂Fe₂(μ-B₄N₄H₈)-Iso1-singlet	0.293	0	0.295	0	0.295	0
Cp₂Fe₂(μ-B₄N₄H₈)-Iso1-triplet	0.295	88.7	0.293	51.1	0.297	82.1
Cp₂Fe₂(μ-C₈H₈)-singlet	0.294	0	0.298	0	0.295	0
Cp₂Fe₂(μ-C₈H₈)-triplet	0.343	79.5	0.348	7.8	0.346	71.7

Theoretical Studies on the Bonding Properties of Metal-metal Multiple Bond of Cp₂M₂(μ-B₄N₄H₈)(M=V,Cr,Mn,Fe)^†

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References 29

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