Metal carbonyl-phosphorus trifluoride systems. V. Decacarbonyldimanganese

Abstract

De, ev Cu3 (linear) 2.3 2.84 Cus (triangular) 2.3 2.24Cu,i (square planar) 2.3 (adjacent atoms) 3.11 Cue (octahedral) 2.4 (from center of inversion) 3.6Clementi and Raimondi16 or by Slater's20 rules, were found to be inadequate.21The traditional transition metal basis set of 3d, 4s, and 4p orbitals proved to be optimum for the description of the Cu2 molecule. The lowest filled molecular orbitals, which are largely 3d in character, were important in accounting for the core repulsions at short distances and were extremely important for the calculation of the stretching frequency, coe. The inclusion of the higher lying 4p orbitals in the basis set was important for the calculation of the spectral transition, , since the 4s-4ps mixing effectively lowers the energy of the * orbital. The 4s orbitals were the most important ones since all molecular properties of Cu2 are largely dependent upon them.The energy and core repulsion in the Cusachs approximation varies as S2/(l + S) at short internuclear distances. This dependence approximates the core repulsions of Cu2 and gives the best reproduction of the (20) J. C. Slater, Phys. Rev., 36, 57 (1930). ( 21) We have found that calculations using double valence orbital basis sets yield results that are nearly identical with those using single orbital exponents; hence, only the latter were used here.

Metallacyclohexadiene and metallabenzene chemistry. 3. Synthesis, characterization, and reaction chemistry of a family of 1-iridacyclohexa-2,4-diene complexes

“…Found: C, 39.37; , 7.07. Solution NMR experiments of 2 were done at -50 °C, because signals were broad at higher temperature. NMR ((CD3)2CO, -50 °C): b 5.65 (br t, JH-p = 22 Hz, 1, HI), 5.05 (br s, 1, H3), 2.68, 2.55 (s's, 2, H5's), 2.35,1.37 (s's, 2X3, pentadienyl CHg's), 2.05 (br m, 18, PEtg CH2's), 1.10 (br m, 27, PEtg CHg's). 130| | NMR -50 °C): b -19.9 (t, JP.P = 14 Hz, 1), -29.7 (t, JP-P = 14 Hz, 1), -36.8 (t, Jp-p = 14 Hz, 1).…”

“…Synthesis of [(irCH=C(Me)CH=C(Me)CH2)(PEt3)g-(CO)]+OgSCFg- (5). Compound 2 (0.40 g, 5.1 X 10'4 mol) was dissolved in 20 mL of acetone and the solution cooled to -78 °C in a dry ice-acetone bath.…”

“…Compound 1 can be cleanly converted to the cationic metallacycle [(IrCH=C(Me)-CH=C(Me)CH2)(PEt3)3]+03SCF3" (2), which serves as the precursor to a large family of new l-iridacyclohexa-2,4diene complexes. Furthermore, treatment of 2 with lithium diisopropylamide (LDA) in acetone leads to the production of (Ir^CH^C(Me)^CH^C(Me)^CH)(PEt3)3 (9), a rare example of a stable metallabenzene.5 Two (5) The only other stable metallabenzene was obtained by Roper via a cyclization reaction involving acetylene and an osmium-thiocarbonyl complex. However, the six-membered ring in this compound possessed a sulfido substituent, which coordinated to the metal center and possibly stabilized the structure.…”

Reactions of fluorocarbon-bridged di(tertiary phosphines and arsines) with manganese and rhenium carbonyls

“…The number of structures, that one can think of, is immense, and this paper, therefore, does not attempt to cover the subject exhaustively. Rather, it takes as its starting point certain bridged complexes, which have been illucidated by structure analyses, and uses these to illustrate the way of going about the augmentation of the standard nomenclature for their skeletons.2 A recent IUPAC publication213 3 proposed the symbols and for characterizing configurational chirality (1) (3) International Union of Pure and Applied Chemistry, Information Bulletin No. 33, 1968; Inorg.…”