Distorted tetrahedral molecules

All these compounds have (distorted) tetrahedral molecules, those of formula O2SX2 having C2v symmetry and the others Cj. Dimensions are in Table 15.15 the remarkably short O-S and S-F distances in O2SF2 should be noted (cf. above). Indeed, the implied strength of bonding in this molecule is reflected by the fact that it can be made by reacting the normally extremely inert compound SFg (p. 687) with the fluoro-acceptor SO3 ... 

Discrete tetrahedral [MntFRjl l complexes have apparently not been prepared, but Mn(PRj)2l2 consists of distorted tetrahedral molecules. As wc shall sec (Chapter 11) phosphine complexes with targe positive charges on the transition metal will be less stable than when there is more electron density on the metal, as in the (B2P2Ji layer. The present MO discussion and the MO diagram above anticipate the discussion of molecular orbital theory in complexes in Chapter 11 and may most profitably be read again after reading that chapter. 

Both Be-N (1.90, 1.92 A) and Be-C (1.81, 1.85 A) distances in dimethyl-bis(quinuclidine)beryllium are longer than those in the previous compound. The lengthening can be ascribed to the steric influence of the bulky ligands. The relatively smaller degree of lengthening in the Be-C bonds could account for the large Me-Be-Me angle of 118°, compared with 111° for N-Be-N, in this distorted tetrahedral molecule. 

Fig. 2. Structures for the solid (a) fee Cco, (b) fee MCco, (c) fee M2C60 (d) fee MsCeo, (e) hypothetical bee Ceo, (0 bet M4C60, and two structures for MeCeo (g) bee MeCeo for (M= K, Rb, Cs), and (h) fee MeCeo which is appropriate for M = Na, using the notation of Ref [42]. The notation fee, bee, and bet refer, respectively, to face centered cubic, body centered cubic, and body centered tetragonal structures. The large spheres denote Ceo molecules and the small spheres denote alkali metal ions. For fee M3C60, which has four Ceo molecules per cubic unit cell, the M atoms can either be on octahedral or tetrahedral symmetry sites. Undoped solid Ceo also exhibits the fee crystal structure, but in this case all tetrahedral and octahedral sites are unoccupied. For (g) bcc MeCeo all the M atoms are on distorted tetrahedral sites. For (f) bet M4Ceo, the dopant is also found on distorted tetrahedral sites. For (c) pertaining to small alkali metal ions such as Na, only the tetrahedral sites are occupied. For (h) we see that four Na ions can occupy an octahedral site of this fee lattice.

Actually, symmetrical tetrahedral molecules like methane do have extremely small dipole moments, caused by centrifugal distortion effects these moments are so small that they can be ignored for all practical purposes. For CH4, p is 5.4 x 10 D Ozier, I. Phys. Rev. Lett., 1971, 27, 1329 Rosenberg, A. Ozier, I. Kudian, A.K. J. Chem. Phys., 1972, 57, 568. 

Blue copper proteins. A typical blue copper redox protein contains a single copper atom in a distorted tetrahedral environment. Copper performs the redox function of the protein by cycling between Cu and Cu. Usually the metal binds to two N atoms and two S atoms through a methionine, a cysteine, and two histidines. An example is plastocyanin, shown in Figure 20-29Z>. As their name implies, these molecules have a beautiful deep blue color that is attributed to photon-induced charge transfer from the sulfur atom of cysteine to the copper cation center. 

Loosely packed unassociated molecules. The 209b Sn atoms have slightly distorted tetrahedral configuration. The same structure is prevalent also at 110 K. The behaviour of solid Me3SnCl is different (see 33 in Table 5). 

More recently, tetranuclear complexes, related to those previously obtained for both ruthenium and osmium, have been obtained for iron, and their structures have been established by X-ray analysis 118). The reported adducts are [Fe4(CO)11(RC2R1)2] (R = H, R1 = Me, Et, n-Pr R = R1 = Me), and are obtained in very low yield (<1%). For R = H, R1 = C2H5, the structure is shown in Fig. 16. This involves a distorted tetrahedral metal system with the two alkyne groups bonding in a manner similar to that observed for the "butterfly molecule [Co4(CO)10(EtC2Et)] 119). 

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