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Appreciably bent sp carbon chains : synthesis, structure and protonation of organometallic 1,3,5-triynes and 1,3,5,7-tetraynes of the formula (η5-C5Me5)Re(NO)(PPh3)((C=C) n- p-C6H4Me).

Autorzy

Roman Dembiński

Tadeusz Lis

Sławomir Szafert

Ch. I. Mayne

T. Bartik

John A. Gladysz

Rok wydania

1999

Czasopismo

Journal of Organometallic Chemistry

Numer woluminu

578

Strony

229-246

DOI

10.1016/S0022-328X(98)01128-0

Kolekcja

Naukowa

Język

Angielski

Typ publikacji

Artykuł

Streszczenie

The diyne (η5-C5Me5)Re(NO)(PPh3)(CCCCSiMe3) is elaborated to (η5-C5Me5)Re(NO)(PPh3)(CCCCCCSiR3) (R=Me, 3a; Et, 3b) by sequences involving n-Bu4N+F− in aqueous THF to give (η5-C5Me5)Re(NO)(PPh3)(CCCCH) (91%), n-BuLi/CuI or t-BuOCu to give (η5-C5Me5)Re(NO)(PPh3)(CCCCCu) (4), and coupling with ICCSiMe3 (48%) or BrCCSiEt3 (84–65%). Complex 3b is similarly converted to (η5-C5Me5)Re(NO)(PPh3)(CCCCCCH) (88%) and (η5-C5Me5)Re(NO)(PPh3)(CCCCCCCu) (6). Reactions of 4 and 6 with BrCC-p-C6H4Me give the title compounds (η5-C5Me5)Re(NO)(PPh3)((CC)n-p-C6H4Me) (n=3, 7; 4, 8; 77–66%). Optimized one flask conversions of 1a and 3b to 7 (81%) and 8 (71%) are described. The crystal structures of 7 (monoclinic, P21/c, a/b/c=17.951(8)/8.377(5)/22.160(9) Å, β=103.63(5)°, Z=4), and 8 (monoclinic, P21/n, a/b/c=8.426(3)/16.400(6)/25.400(9) Å, β=97.51(3)°, Z=4) show markedly curved sp carbon chains—much more than hexatriynes or octatetraynes reported to date. The bond angles associated with the Re(CC)nC moieties (min/max/avg) are 169.1(10)°/178.8(13)°/174.7° (7) and 170.0(9)°/178.8(10)°/175.7° (8). Other structural features are normal, and bending is provisionally ascribed to packing forces. Reaction of 7 and HBF4·OEt2 gives the cationic vinylidene complex [(η5-C5Me5)Re(NO)(PPh3)(CC(H)CCCC-p-C6H4Me)]+BF4−, the structure of which is established by extensive NMR analyses.

Adres publiczny

https://doi.org/10.1016/S0022-328X(98)01128-0

Strona internetowa wydawcy

http://www.elsevier.com

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