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

Info iconThis preview shows page 1. Sign up to view the full content.

View Full Document Right Arrow Icon
This is the end of the preview. Sign up to access the rest of the document.

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...
View Full Document

Ask a homework question - tutors are online