G fe ni cu ptwhite phosphorus but and c o c o

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Unformatted text preview: C O ) ~ ) ~ { ~ , ~ ~ - ( C R ) ~ } ] cence (e.g. Fe, Ni, Cu, Pt).White phosphorus (but and [ { C O ( C O ) ~ } Z ( ~ , ~ ~ ItAwas )formed by - S~ ]. not red) also reacts readily with heated aqueous reaction of Na[Co(CO),] with PC13 or PBr3 solutions to give a variety of products (pp. 493 in thf. The tetrahedrane-like core (Fig. 12.7a) and 513ff), and with many other aqueous and was confirmed by X-ray analysis on the related nonaqueous reagents. PPh3 derivative [Co~(CO)s(PPh3)(p,q~-Pz)l.(~~) The stereochemistry and bonding of P are very Direct action of P4 with appropriate carbonyl, varied as will become apparent in later sections: cyclopentadienyl or alkoxide derivatives of the element is known in at least 14 coordination Cr, Mo, W, etc. has yielded a wide range geometries with CN up to 9, though the most of such compounds of P2 acting as a frequently met have CN 3,4, 5 and 6. Some typ4e-donor, in all of which the two ML, ical coordination geometries are summarized in vertices can be considered as 15e-acceptors Table 12.2 and illustrated in Fig. 12.6. Many of (i.e d” 5e, “isoelectronic” with P in Group these compounds will be more fully discussed in 15) e.g., IC~(CP)(CO>Z},(~~) IMO(CP)(CO)~}, later sections. { W(py)(OPi )2 (p-OPr‘)) (47), etc., where Cp is The great propensity of P atoms to catenate (q5-C5H5) or one of its derivatives. With into chains, rings and clusters, P,, has already 14e or 16e metal-vertex acceptors the core been noted during the discussion on allotropy adopts the more open “butterfly” configuration (pp. 479-83). These groupings and other similar (Fig 12.7b) without direct M-M bonding, ones also feature in the structures of metal e.g [ { Ni(Et2PCH2CH2PEt2)}2(p, q2-P2)l(48) and phosphides (p. 489), polyphosphanes (p. 492) its {Ni(PEt3)2} and [Pt(PEt3)2] analogues. and organopolyphosphanes (p. 542). Moreover, Further electron-pair donation from one or neutral or charged groupings, P,, ( n = 2-6, 10) both of the P atoms can also occur to give can also serve as ligand^(^'-^), as can isolated P atoms in anions such as [ ( ~ ~ - ~ ) { ~ ~ ( ~ ~ compounds ~ ~ 4 0[~ ) ~ } 6 ] such as Cr2(qS-C5H5)2(C0)4(p,q2P ~)IM(CO)~JI2 3 (M = Cr, Mo, W) (see or and other structures shown at the foot of Figs. 12.7 c, d).(49) In these, the Pz group acts Fig. 12.6. Two decades ago virtually nothing as a 6e or 8e donor, and bridges 3 or 4 M was known about this aspect of phosphorus atoms respectively. See below - p. 488 - for chemistry, but it is now a burgeoning field, and examples cf. bis-P2, i.e. pseudo-P4 complexes.) the substantial progress which has been made in recent years now permits a general overview to 45 C. F. CAMPANA, VIU-OROSZ, PALYI, . MARKO nd A. G. L a be given. + L. F. DAHL, norg. Chem. 18, 3054-9 (1979). Z 46 L. Y. GOH,C. K. CHU,R. C. S . WONG and T. W. HAMB- 42 M. DI VAIRAand P. STOPPION,olyhedron 6, 35 1-82 P (1987). (Review) 4 3 0. J. SCHERER, Angew. Chem. Int. Edn. Engl. 24, 924-43 (1985); 29 1104-22 (1990). (Reviews) 4 40.. SCHERER 9 others), in R. STEUDEL J (and (ed.), The Ch...
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This note was uploaded on 10/12/2012 for the course CHEMISTRY CHM1040 taught by Professor Jhon during the Spring '12 term at Florida A&M.

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