Supporting Information - Part 2

A Mechanistic Foray into the Chemistry of Metallabenzenes: Formation, Reactivity and Formal Oxidation State

Mark A. Iron, André C. B. Lucassen, Hagai Cohen, Milko E. van der Boom* and Jan M.L. Martin*

Journal of the American Chemical Society 126, 11699-11710 (2004)

DOI: http://dx.doi.org/10.1021/ja047125e

Supporting Information - Part 2

(click here for Part 1 of the Supporting Information in .pdf file format) (click here for all the geometries in text file format)

Below are the calculated structures (mPW1K/SDD) of the various complexes and transition states. Each is given is two formats, .xyz and JMOL. The latter allows one to view and manipulate the structures in one's web browser. (Jmol is an open-source cross-platform molecular viewer written in Java that reproduces the functionality of RASMOL/CHIME. For more information about JMol see http://jmol.sourceforge.net; to rotate a molecule, move the mouse on it; to zoom, use the scroll wheel; for more options, right-click on the molecule view.)

Certain complexes were not explicity numbered in the paper:

Transition states are labelled as TS(x-y) where x and y are the complexes the transition state connects.
In the Cp-formation, only the metallabenzene complex was numbered. The other complexes are identified by the parent metallabenzene number appended by "a" for the transistion state, "b" for the inital product and "c" for the final product (where applicable). In the cases of 20 and 21 where additional geometries were found, descriptive suffices are added.
The para-substituted metallabenzenes are identified as above but with the substituted appended to the end of the label.
In the formation of the osmabenzene 1, the intermediate in the alternate route involving dissociation of the second phosphine and acetlyene-acetylene coupling prior to CS coupling are labelled as 55 through 78.
In the formation of the iridiabenzene 50, the complex trans-(PH₃)₂Ir(CO)Cl is labelled as 59.

17COOH xyz jmol

17Cl xyz jmol

17NH2 xyz jmol

17NO2 xyz jmol

17OMe xyz jmol

17a xyz jmol

17aCOOH xyz jmol

17aCl xyz jmol

17aNH2 xyz jmol

17aNO2 xyz jmol

17aOMe xyz jmol

17b xyz jmol

17bCOOH xyz jmol

17bCl xyz jmol

17bNH2 xyz jmol

17bNO2 xyz jmol

17bOMe xyz jmol

17c xyz jmol

18COOH xyz jmol

18Cl xyz jmol

18NH2 xyz jmol

18NO2 xyz jmol

18OMe xyz jmol

18a xyz jmol

18aCOOH xyz jmol

18aCl xyz jmol

18aNH2 xyz jmol

18aNO2 xyz jmol

18aOMe xyz jmol

18b xyz jmol

18bCOOH xyz jmol

18bCl xyz jmol

18bNH2 xyz jmol

18bNO2 xyz jmol

18bOM2 xyz jmol

19Cl xyz jmol

19NH2 xyz jmol

19NO2 xyz jmol

19OMe xyz jmol

19a xyz jmol

19aCOOH xyz jmol

19aCl xyz jmol

19aNH2 xyz jmol

19aNO2 xyz jmol

19aOMe xyz jmol

19b xyz jmol

19bCOOH xyz jmol

19bCl xyz jmol

19bNH2 xyz jmol

19bNO2 xyz jmol

19bOMe xyz jmol

19c xyz jmol

19cCOOH xyz jmol

19cCl xyz jmol

19cNH2 xyz jmol

19cNO2 xyz jmol

19cOMe xyz jmol

20NH2 xyz jmol

20NO2 xyz jmol

20a xyz jmol

20aNH2 xyz jmol

20aNO2 xyz jmol

20b xyz jmol

20bNH2 xyz jmol

20bNO2 xyz jmol

20bcistrans xyz jmol

20c xyz jmol

20cNH2 xyz jmol

20cNO2 xyz jmol

21a xyz jmol

21b xyz jmol

21bcistrans xyz jmol

21c xyz jmol

21cPH3loss xyz jmol

22a xyz jmol

22b xyz jmol

23a xyz jmol

23b xyz jmol

24a xyz jmol

24b xyz jmol

24c xyz jmol

25a xyz jmol

25b xyz jmol

25c xyz jmol

26NH2 xyz jmol

26NO2 xyz jmol

50Pt xyz jmol

26a xyz jmol

26aNH2 xyz jmol

26aNO2 xyz jmol

26bNH2 xyz jmol

28cNH2 xyz jmol

26bNO2 xyz jmol

26cNO2 xyz jmol

26b xyz jmol

28c xyz jmol

27a xyz jmol

27b xyz jmol

27c xyz jmol

28NH2 xyz jmol

28NO2 xyz jmol

28a xyz jmol

28aNH2 xyz jmol

28aNO2 xyz jmol

28b xyz jmol

28bNH2 xyz jmol

28bNO2 xyz jmol

29NH2 xyz jmol

29NO2 xyz jmol

29a xyz jmol

29aNH2 xyz jmol

29aNO2 xyz jmol

29b xyz jmol

29bNH2 xyz jmol

29bNO2 xyz jmol

30a xyz jmol

30b xyz jmol

29c xyz jmol

31NH2 xyz jmol

31NO2 xyz jmol

31a xyz jmol

31aNH2 xyz jmol

31aNO2 xyz jmol

31b xyz jmol

31bNH2 xyz jmol

31bNO2 xyz jmol

32a xyz jmol

32b xyz jmol

33a xyz jmol

33bNH2 xyz jmol

33b xyz jmol

34c xyz jmol

33cNH2 xyz jmol

33cNO2 xyz jmol

34a xyz jmol

34b xyz jmol

41-42 xyz jmol

41-42co xyz jmol

42-43 xyz jmol

42co-43co xyz jmol

42co xyz jmol

43co xyz jmol

44-45 xyz jmol

44co-45co xyz jmol

44co xyz jmol

45-38 xyz jmol

45co xyz jmol

47a xyz jmol

47aMe xyz jmol

47b-48 xyz jmol

47b xyz jmol

47bMe-48Me xyz jmol

47bMe xyz jmol

48-50 xyz jmol

48Me-50Me xyz jmol

48Me xyz jmol

48Pt-50Pt xyz jmol

48Pt xyz jmol

49-50 xyz jmol

50Me xyz jmol

56-57 xyz jmol

58-45 xyz jmol