TY - JOUR
T1 - A Distibene with Extremely Long Sb=Sb Distance and Related Heavier Dipnictenes from Salt-Free Metathesis Reactions
AU - Roller, Clara A.
AU - Doler, Berenike
AU - Steller, Beate Gabriele
AU - Saf, Robert
AU - Fischer, Roland C.
PY - 2023/12/20
Y1 - 2023/12/20
N2 - Conversions of organoelement diamides, Ar
DippE(NMe
2)
2 (E=Sb, Bi; Ar
Dipp=C
6H
3-2,6-Dipp
2), with Ph
2SnH
2 as reducing agent gave access to low-valent, heavier group 15 dimers Ar
DippSb=SbAr
Dipp and Ar
DippBi=BiAr
Dipp, while only readily removable byproducts (i. e. dihydrogen, amines) and cyclo-(Ph
12Sn
6) are generated during the reaction. Moreover, experiments involving the reaction of organoantimony hydride species Ar*
2SbH (Ar*=C
6H
2-2,6-(Ph
2CH)
2-4-iPr) with Bi(NEt
2)
3 yielded a second novel distibene, Ar*Sb=SbAr*, with the currently longest Sb−Sb bond distance of 2.8605(5) Å in a distibene. In conversions of TbbSnH
3 (Tbb=C
6H
2-2,6-(CH(SiMe
3)
2)
2-4-tBu) with Bi(NEt
2)
3, ligand migration resulted in the isolation of TbbBi=BiTbb. Remarkably, the herein reported novel inorganic coupling route enables preparation and isolation of heavier dipnictenes without the formation of inorganic salts. All four low-oxidation state compounds were isolated and subsequently characterized using state of the art techniques, i. e. X-ray crystallography, NMR and UV/Vis spectroscopy.
AB - Conversions of organoelement diamides, Ar
DippE(NMe
2)
2 (E=Sb, Bi; Ar
Dipp=C
6H
3-2,6-Dipp
2), with Ph
2SnH
2 as reducing agent gave access to low-valent, heavier group 15 dimers Ar
DippSb=SbAr
Dipp and Ar
DippBi=BiAr
Dipp, while only readily removable byproducts (i. e. dihydrogen, amines) and cyclo-(Ph
12Sn
6) are generated during the reaction. Moreover, experiments involving the reaction of organoantimony hydride species Ar*
2SbH (Ar*=C
6H
2-2,6-(Ph
2CH)
2-4-iPr) with Bi(NEt
2)
3 yielded a second novel distibene, Ar*Sb=SbAr*, with the currently longest Sb−Sb bond distance of 2.8605(5) Å in a distibene. In conversions of TbbSnH
3 (Tbb=C
6H
2-2,6-(CH(SiMe
3)
2)
2-4-tBu) with Bi(NEt
2)
3, ligand migration resulted in the isolation of TbbBi=BiTbb. Remarkably, the herein reported novel inorganic coupling route enables preparation and isolation of heavier dipnictenes without the formation of inorganic salts. All four low-oxidation state compounds were isolated and subsequently characterized using state of the art techniques, i. e. X-ray crystallography, NMR and UV/Vis spectroscopy.
KW - Main group chemistry
KW - P-block elements
KW - Single crystal X-ray diffraction
KW - NMR spectroscopy
KW - Antimony
KW - Bismuth
KW - X-ray diffraction
KW - Hydrides
KW - Main-group elements
UR - http://www.scopus.com/inward/record.url?scp=85180178074&partnerID=8YFLogxK
U2 - 10.1002/ejic.202300586
DO - 10.1002/ejic.202300586
M3 - Article
SN - 1434-1948
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
M1 - e202300586
ER -