Synthese und Charakterisierung von binären Molekülverbindungen der Gruppe 15 Elemente mit P₂As₂‐, PSb₂‐, PBi₂‐, PBi₃‐ und P₂Bi₄‐Gerüst

Abstract

. Synthese und Charakterisierung von binären Molekülverbindun-gen der Gruppe 15 Elemente mit P2As2-, PSb2-, PBi2-, PBi3-und P2Bi4-Gerüst. Zeitschrift für Anorganische und Allgemeine Chemie, 2009, 635 (13-14)

Building Chains – Three Different Pnictogen Atoms in an Entirely tert‐Butyl Substituted Molecule

“…The P, As and Sb atoms all have a distorted trigonal‐pyramidal environment with sums of angles of 318.2(1)° at As, 330.3(1)° at P and 316.2(1)° at Sb. The As–P, Sb–P and P–C bond lengths and the interpnictogen angle As–P–Sb are similar to those observed in the cations [(R 3 As) 2 PMe] 2+ (R = Me, Ph) and the Sb 2 P chain compound t BuPh 2 SiP[Sb(Cl)CH(SiMe 3 ) 2 ] 2 , , . Owing to the orientation of the sterically demanding substituents around the P atom, three different angles are observed: 119.0(1)° between the t Bu 2 Sb and t Bu units, 110.66(3)° between the t Bu 2 As and t Bu 2 Sb substituents and 100.6(1)° between the t Bu and t Bu 2 As groups (Figure ).…”

“…The angles for 3 vary from the small C-P-As angle with 100.18(9)°to the largest As-P-Li angle with 126.1(1)°. Similar C-P-Sb and Sb-P-Li angles of 101.88(5)°and 125.97 (7)°are observed for 4. The Sb-P bond in 4 is 248.67(4) pm long, whereas the As-P bond length in 3 is only 229.83 (7) pm.…”

“…As in 7 , for all heteroatoms a distorted trigonal‐pyramidal environment is observed. The Sb–P bond lengths do not differ from those of the known Sb 2 P chain molecule t BuPh 2 SiP[Sb(Cl)CH(SiMe 3 ) 2 ] 2 . The substituents on the phosphorus atom are arranged in the same way as already described for 7 , and even the angles are akin.…”

“…Crystallographically characterized stibaphosphanes are less frequent compared to arsaphosphanes. Worth mentioning are the polycyclic compounds (ThexMe 2 SiP) 4 Sb 4 and Sb 2 (PSi t BuPh 2 ) 4 as well as the open‐chain Sb–P–Sb compound t BuPh 2 SiP[Sb(Cl)CH(SiMe 3 ) 2 ] 2 , . To the best of our knowledge, no organic‐substituted interpnictogen compounds are known that contain three different group 15 elements (excluding nitrogen) bound to each other.…”

“…[5] An all-trans configuration of the substituents is observed in the four-membered As 2 P 2 ring compounds [{Cp*(CO) 2 FeAs} 2 (MesP) 2 ] and [(tBuPh 2 SiP) 2 {(Me 3 Si) 2 CHAs} 2 ]. [6,7] Radial triarsaphosphanes P[As{C(O)R} 2 ] 3 (R = tBu, Ph), synthesized by Jones et al, bear three phenyl-or tert-butyl-diacylarsenido substituents on the phosphorus atom. [8,9] Cationic As-P compounds were described by Burford et al For example, the cations [R 3 AsP(Me)AsR 3 ] 2+ (R = Me, Ph) were obtained from…”