TY - JOUR

T1 - 2,2′-Azobispyridine in Phosphorus Coordination Chemistry

T2 - A New Approach to 1,2,4,3-Triazaphosphole Derivatives

AU - Panova, Yulia S.

AU - Sheyanova, Alexandra V.

AU - Zolotareva, Nataliya V.

AU - Sushev, Vyacheslav V.

AU - Arapova, Alla V.

AU - Novikov, Alexander S.

AU - Baranov, Evgenii V.

AU - Fukin, Georgy K.

AU - Kornev, Alexander N.

PY - 2018/10/17

Y1 - 2018/10/17

N2 - Oxidative addition of 2,2′-azobispyridine (abpy) to PCl3 in CH2Cl2 or THF gave the 1:1 addition product, containing phosphorus in high oxidation state (+5) and a reduced form of the ligand. 2,2′-Hydrazobispyridine (hbpy) was prepared by reduction of abpy with hydrazine-hydrate in 63 % yield. Interaction of hbpy with PCl3 in the presence of triethylamine gave (abpy)2–PCl (2) in 25 % preparative yield. A similar reaction of hbby with (Et2N)2PCl afforded (abpy)2–PNEt2 (4) in 89 % yield. Compound 4 after work-up with PCl3 or PBr3 gave 2 and (abpy)2–PBr (6) respectively in high yields. Diethylamino-derivative 4 formed (κ2-N,N) adduct with SiCl4 7 (coordination by Py and azo-functions), while the chloro-derivative 2 did not. Reaction of 2 with PCl5 is accompanied with liberation of PCl3 and formation of spirocyclic ate complex [(abpy)2– 2P]+PCl6 –. All structurally characterized compounds demonstrated short distances between pyridyl nitrogen and the phosphorus atom. However, the QTAIM analysis did not reveal the presence of appropriate bond critical points (3, –1) for the intramolecular noncovalent interactions N···P in 2, 4, and 6. We theoretically estimated values of the rotation barriers for the pyridyl and Et2N moieties in 4 using the relaxed potential energy surface scan at the B3LYP/6-31G(d) level of theory. The values of rotation barriers are very close to each other, viz. 13.2 (pyridyl) and 13.0 (Et2N) kcal/mol.

AB - Oxidative addition of 2,2′-azobispyridine (abpy) to PCl3 in CH2Cl2 or THF gave the 1:1 addition product, containing phosphorus in high oxidation state (+5) and a reduced form of the ligand. 2,2′-Hydrazobispyridine (hbpy) was prepared by reduction of abpy with hydrazine-hydrate in 63 % yield. Interaction of hbpy with PCl3 in the presence of triethylamine gave (abpy)2–PCl (2) in 25 % preparative yield. A similar reaction of hbby with (Et2N)2PCl afforded (abpy)2–PNEt2 (4) in 89 % yield. Compound 4 after work-up with PCl3 or PBr3 gave 2 and (abpy)2–PBr (6) respectively in high yields. Diethylamino-derivative 4 formed (κ2-N,N) adduct with SiCl4 7 (coordination by Py and azo-functions), while the chloro-derivative 2 did not. Reaction of 2 with PCl5 is accompanied with liberation of PCl3 and formation of spirocyclic ate complex [(abpy)2– 2P]+PCl6 –. All structurally characterized compounds demonstrated short distances between pyridyl nitrogen and the phosphorus atom. However, the QTAIM analysis did not reveal the presence of appropriate bond critical points (3, –1) for the intramolecular noncovalent interactions N···P in 2, 4, and 6. We theoretically estimated values of the rotation barriers for the pyridyl and Et2N moieties in 4 using the relaxed potential energy surface scan at the B3LYP/6-31G(d) level of theory. The values of rotation barriers are very close to each other, viz. 13.2 (pyridyl) and 13.0 (Et2N) kcal/mol.

KW - 2,2′-Azobispyridine

KW - Azaphospholes

KW - Azo compounds

KW - Noncovalent interactions

KW - Phosphorus heterocycles

KW - POSITIONAL ISOMERISM

KW - MOLECULAR-STRUCTURE

KW - COMPLEXES

KW - CRYSTAL

KW - ADDUCTS

KW - 2,2 '-Azobispyridine

KW - HYPERVALENT

KW - HETEROCYCLES

KW - ORGANOTIN(IV) DERIVATIVES

KW - BONDS

KW - 2,2-AZOPYRIDINE

UR - http://www.scopus.com/inward/record.url?scp=85053899016&partnerID=8YFLogxK

U2 - 10.1002/ejic.201800831

DO - 10.1002/ejic.201800831

M3 - Article

AN - SCOPUS:85053899016

VL - 2018

SP - 4245

EP - 4254

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

IS - 38

ER -