Cp2Zr(η2-benzocyclobutadiene)(PMe3), a rare η2-cyclobutadiene complex

Organometallics

Volumn 21, Issue 26, 2002, Pages 5685-5687

  Ramakrishna, T V V ^a   Lushnikova, Svetlana ^a   Sharp, Paul R ^a  

^a UNIVERSITY OF MISSOURI   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXES;

COMPLEXATION; DERIVATIVES; HYDROGEN BONDS; MOLECULAR STRUCTURE; OLEFINS; PYROLYSIS;

ORGANOMETALLICS;

EID: 0038678621     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om020829h     Document Type: Article

References (34)

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4. (a) Choukroun, R.; Cassoux, P. Acc. Chem. Res. 1999, 32, 494-502.
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8. Aldrich Chemical Co. Catalog.
9. Reviews on cyclobutadiene complexes: (a) Baker, P. K.; Silgram, H. Trends Organomet. Chem. 1999, 3, 21-33.
10. (b) Efraty, A. Chem. Rev. 1977, 77, 691-744.
11. 2 (SHELXL) to R1 = 0.0413. Selected distances (A) and angles (deg): Zr1-P1 = 2.7022(9), Zr1-C1 = 2.346(3), Zr1-C2 = 2.339(3), C1-C2 = 1.526(4), C1-C7 = 1.502(4), C2-C8 = 1.510(4), C3-C8 = 1.376(4), C6-C7 = 1.377(4), C7-C8 = 1.412(4); C2-Zr1-C1 = 38.01(11), C2-C1-Zr1 = 70.75(16), C2-C1-C7 = 87.9(2), C7-C1-Zr1 = 113.27(19), C1-C2-C8 = 87.8(2), C1-C2-Zr1 = 71.24(16), C8-C2-Zr1 = 113.14(19), C4-C3-C8 = 116.4(3), C3-C4-C5 = 121.8(3), C4-C5-C6 = 121.7(3), C5-C6-C7 = 116.4(3), C1-C7-C6 = 145.8(3), C1-C7-C8 = 92.4(2), C6-C7-C8 = 121.8(3), C2-C8-C3 = 146.2(3), C2-C8-C7 = 91.9(2), C3-C8-C7 = 121.9(3).
12. 2-cyclobutadiene complex has been reported: Winter, W.; Strähle, J. Angew. Chem., Int. Ed. Engl. 1978, 17, 128-129.
13. 2-cyclobutadiene complexes: (a) Sanders, A.; Giering, W. P. J. Organomet. Chem. 1976, 104, 49-65.
14. (b) Sanders, A.; Magatti, C. V.; Giering, W. P. J. Am. Chem. Soc. 1974, 96, 1610-1611.
15. Fisher, R. A.; Buchwald, S. L. Organometallics 1990, 9, 871-873.
16. (a) Negishi, E.; Takahashi, T. Rev. Heteroat. Chem. 1992, 6, 177-201.
17. (b) Steigerwald, M. L.; Goddard, W. A., III. J. Am. Chem. Soc. 1985, 107, 5027-5035.
18. (a) Chapman, O. L.; Chang, C. C.; Rosenquist, N. R. J. Am. Chem. Soc. 1976, 95, 261-262.
19. (b) Winter, W.; Straub, H. Angew. Chem., Int. Ed. Engl. 1978, 17, 127-128 and references therein.
20. 3 by exposing the reaction mixture to vacuum maximizes the yield and purity of 3.
21. 2 (SHELXL) to R1 = 0.1101. Selected distances (A) and angles (deg): Zr1-C11 = 2.250(12), Zr1-C26 = 2.298(10), C11-C12 = 1.527(17), C11-C18 = 1.631(15), C12-C13 = 1.47(2), C12-C17 = 1.475(19), C13-C14 = 1.26(2), C14-C15 = 1.33(2), C15-C16 = 1.35(2), C16-C17 = 1.51(2), C17-C18 = 1.482(17), C18-C19 = 1.535(15), C19-C26 = 1.347(14), C11-Zr1 = C26 87.9(4); C12-C11-C18 = 86.1(8), C12-C11-Zr1 = 119.0(9), C18-C11-Zr1 = 100.0(6), C13-C12-C17 - 114.1(14), C13-C12-C11 = 153.0(14), C17-C12-C11 = 92.2(10), C14-C13-C12 = 119.4(16), C13-C14-C15 = 127.8(17), C14-C15-C16 = 119.1(18), C15-C16-C17 = 116.8(18), C12-C17-C18 = 93.7(11), C12-C17-C16 = 119.0(14), C18-C17-C16 = 147.1(15), C17-C18-C19 = 114.6(10), C17-C18-C11 = 87.9(9), C19-C18-C11 = 121.7(9), C26-C19-C20 = 124.2(9), C26-C19-C18 = 123.9(9), C20-C19-C18 = 111.8(9), C19-C26-C27 = 122.6(9), C19-C26-Zr1 = 106.3(7), C27-C26-Zr1 = 131.0(7).
22. (a) Fagan, P. J.; Nugent, W. A. J. Am. Chem. Soc. 1988, 110, 2310-2312.
23. (b) Takahashi, T.; Xi, C.; Xi, Z.; Kageyama, M.; Fischer, R.; Nakajima, K.; Negiahi, E. J. Org. Chem. 1998, 63, 6802-6806.
24. 2 (SHELXL) to R1 = 0.0310. Selected distances (A) and angles (deg): Zr1-N1 = 2.0509(17), Zr1-C2 = 2.349(2), N1-C9 = 1.273(3), C1-C9 = 1.523(3), C1-C8 = 1.535(3), C1-C2 = 1.611(3), C2-C3 = 1.499(3), C3-C4 = 1.388(3), C3-C8 = 1.394(3), C4-C5 = 1.391(3), C5-C6 = 1.393(4), C6-C7 = 1.402(4), C7-C8 = 1.377(3); N1-Zr1-C2 = 78.29(8), C9-N1-Zr1 = 122.83(15), C9-C1-C8 = 117.70(17), C9-C1-C2 = 113.00(17), C8-C1-C2 = 85.56(16), C3-C2-C1 = 86.15(15), C3-C2-Zr1 = 123.21(14), C1-C2-Zr1 = 104.94(13), C4-C3-C8 = 121.1(2), C4-C3-C2 = 143.7(2), C8-C3-C2 = 95.18(18), C3-C4-C5 = 116.9(2), C4-C5-C6 = 121.7(2), C5-C6-C7 = 121.4(2), C8-C7-C6 = 116.3(2), C7-C8-C3 = 122.6(2), C7-C8-C1 = 144.5(2), C3-C8-C1 = 92.89(18), N1-C9-C1 = 118.22(19).
25. 2 (SHELXL) to R1 = 0.0413. Selected distances (A) and angles (deg): Zr1-N1 = 2.130(6), Zr1-N2 - 2.152(7), Zr1-C9 = 2.470(7), Zr1-C10 = 2.479(8), N1-C9 = 1.375(10), N1-C15 = 1.497(9), N2- C10 = 1.338(10), N2-C11 = 1.498(10), C1-C9 = 1.529(10), C1-C8 = 1.534(12), C1-C2 = 1.556(15), C2-C3 = 1.568(13), C2-C10 = 1.592(11), C3-C8 = 1.327(14), C3-C4 = 1.409(12), C4-C5 = 1.394(14), C5-C6 = 1.396(17), C6-C7 = 1.326(14), C7-C8 = 1.395(12), C9-C10 = 1.402(11); N1-Zr1-N2 = 89.1(3), N1-Zr1-C9 = 33.8(2), N2-Zr1-C9 = 63.4(2), N1-Zr1-C10 = 64.4(3), N2-Zr1-C10 = 32.6(3), C9-Zr1-C10 = 32.9(3), C9-N1-C15 = 120.8(6), C9-N1-Zr1 = 86.8(4), C15-N1-Zr1 = 148.7(5), C10-N2-C11 = 117.9(8), C10-N2-Zr1 = 87.2(5), C11-N2-Zr1 = 150.7(7), C9-C1-08 = 115.0(7), C9-C1-C2 = 86.4(6), C8-C1-C2 = 89.2(8), C1-C2-C3 = 82.4(8), C1-C2-C10 = 87.9(6), C3-C2-C10 = 115.7(7), C8-C3-C4 = 122.9(10), C8-C3-C2 = 96.7(8), C4-C3-C2 = 140.3(11), C5-C4-C3 = 112.8(12), C4-C5-C6 = 123.4(11), C7-C6-C5 = 121.3(12), C6-C7-C8 = 116.6(12), C3-C8-C7 = 122.9(10), C3-08-01 = 91.6(8), C7-C8-C1 = 145.5(12), N1-C9-C10 = 126.0(6), N1-C9-C1 = 136.2(7), C10-C9-C1 = 96.2(7), N1-C9-Zr1 = 59.4(4), C10-C9-Zr1 = 73.9(4), C1-C9-Zr1 = 137.3(5), N2-C10-C9 = 126.4(7), N2-C10-C2 = 142.6(8), C9-C10-C2 = 89.5(7), N2-C10-Zr1 = 60.2(4), C9-C10-Zr1 = 73.2(4), C2-C10-Zr1 = 136.0(5).
26. Fisher and Buchwald obtained a double t-BuNC insertion product from the cyclobutone complex that may have a similar structure, but in the absence of an X-ray crystal structure determination the complex was formulated as a simple diiminoacyl insertion product.
27. Titanacyclobutane complexes add isocyanides in a similar fashion to produce five-membered rings: Greidanus-Strom, G.; Carter, C. A. G.; Stryker, J. M. Organometallics 2002, 21, 1011-1013.
28. Isocyanide coupling reviews and recent references: (a) Carnahan, E. M.; Protasiewicz, J. D.; Lippard, S. J. Acc. Chem. Res. 1993, 26, 90-97.
29. (b) Durfee, L. D.; Hothwell, I. P. Chem. Rev. 1988, 88, 1059-1079.
30. (c) Ong, T.-G.; Wood, D.; Yap, G. P. A.; Richeson, D. S. Organometallics 2002, 21, 1-3.
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32. (e) Tomaszewski, R.; Lam, K.-C.; Rheingold, A. L.; Ernst, R. D. Organometallics 1999, 18, 4174-4182.
33. (a) Scholz, J.; Dlikan, M.; Stroehl, D.; Dietrich, A.; Schumann, H.; Thiele, K. H. Chem. Ber. 1990, 128, 2279-2285.
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