ET,N-BU) DERIVATIVES AND THEIR RELATIONSHIP TO SOLUTION ISOMERIZATION PROCESSES IN THESE OCTAHEDRAL SPECIES X-RAY STRUCTURAL STUDIES OF CIS-MO(CO)4(PR3)2 (R=ME

The crystal and molecular structures of cis-Mo(CO)4(PMe3)2 (1), cis-Mo(CO)4(PEt3)2 (2), and cis-Mo(CO)4[P(n-Bu)3]2 (3) have been determined for the purpose of seeking correlations between structural featuresespecially evidence of intramolecular strainand reactivity. The main results are as follows. 1: space group P21/n, with unit cell dimensions of a = 9.770 (1) , b = 12.109 (1) , c = 14.183 (1) , = 95.435 (7), V = 1670.5 (5) 3, and Z = 4. The Mo-P distances average 2.522 (1) , and P-Mo-P = 97.54 (4). 2: space group P21/c, with unit cell dimensions of a = 9.740 (3) , b = 16.399 (1) , c = 14.601 (2) , = 109.49 (2), V = 2199 (1) 3, and Z = 4. The Mo-P distances average 2.544 (4) , and P-Mo-P = 100.27 (3). 3: space group P21/c, with unit cell dimensions of a = 20.27 (1) , b = 9.442 (3) , c = 19.011 (6) , = 107.59 (3), V = 3468 (4) 3, and Z = 4. The Mo-P distances average 2.552 (8) , and ZP-Mo-P = 99.29 (4). Within this set of three compounds, there is a fairly good correlation of both steric strain, as evidenced by the P-Mo-P angles, and tendency to isomerize to the trans structure with the steric bulk of the PR3 ligands as indicated by cone angles. However, comparison of structural variations in a total of seven cis-Mo(CO)4(PR3)2 compounds shows that more subtle factors are also at work. 1982, American Chemical Society. All rights reserved.

X-RAY STRUCTURAL STUDIES OF CIS-MO(CO)4(PR3)2 (R=ME,ET,N-BU) DERIVATIVES AND THEIR RELATIONSHIP TO SOLUTION ISOMERIZATION PROCESSES IN THESE OCTAHEDRAL SPECIES Academic Article