1 a) Mo 6 Cp*- 5 Me- 1 2*O= 4 ------------- total 16 Ox state: Cp* - , Me - , 2*O 2- : Mo VI The oxygen atoms also have lone pairs which could do additional -donation to Mo. Could be an OK compound, might associate via bridging oxygens (but the large Cp* might hinder that). b) Cr 6 6*NH 3 12 ------------- total 18 Ox state: Cr (0) Count OK, but ox state low for Cr, and there are no -acceptor ligands, only -donors: this should not be stable. c) Various ways of counting depending on where you put the positive charge and how you draw the bonds (dative vs covalent) to the bridging oxygen. But you should always arrive at two 16-e Pd II
centers. Normal oxidation state and count, should be stable. The drawing suggests there might be a steric problem for the two MeCN molecules, but that is hard to judge from such a simple drawing. d) The tricky part is realizing the B atom must have a negative charge (as in BH 4 - ). This means the Rh must have a corresponding positive charge. Rh 9 2*Py 4 2*C=C 4 + chg -1 ------------- total 16 Ox state: + chg: Rh I Normal oxidation state and count, should be stable. e) For every N atom, one bond to Al must be covalent, the other dative. Al 3 N- 1 N 2 2*Me- 2 ------------- total 8 Ox state: N - , 2*Me - : Al III Normal count, oxidation state and coordination number. Should be OK. You might expect reactivity because of the presence of both acidic NH bonds and reactive Al-C bonds within the same molecule. f) Now all Al-N bonds must be covalent. Al 3 2*N- 2 tBu- 1 ------------- total 6 Ox state: 2*N - , tBu - : Al III Ox state OK, but count low. Would want to form higher aggregates, but the bulky tBu groups might hinder that. There could be some stabilization through NAl - donation, since every N has a lone pair.
2 a) The N-Sn bond must be dative, the other bonds to Sn are covalent: Sn 4 N 2 2*Me- 2 Ar- 1 AcO- 1 ------------- total 10 Four covalent bonds: Sn IV . Sn is large, so counts larger than 8 can occur. b) Somehow the coordinated and dangling Me 2 N group must exchange. If they do, at high temperature you will see for both Me(N) and CH 2 (N) the average of the coordinated and non- coordinated situation. Two reasonable mechanisms are: Sn NMe 2 Me Me Me 2 N OOCMe Sn NMe 2 Me Me Me 2 N OOCMe Sn Me Me Me 2 N OOCMe Me 2 N Sn NMe 2 Me Me NMe 2 + CH 3 COO -
c) The Me(Sn) groups see exactly the same environment before and after the exchange of the Me 2 N groups. So, you will see a singlet (with Sn satellites) for them at any temperature. d) The ionic mechanism sketched above would be accelerated in a polar solvent. The amine dissociation mechanism would probably not be affected. e) Treatment of m-(Me 2 NCH 2 ) 2 C 6 H 4 with BuLi. The coordination of the two amine arms would automatically direct the metallation to the desired position. An alternative would be first making 1-Br-2,6-(Me 2 NCH 2 ) 2 C 6 H 3 , but this might not be easy and would not have any advantage. f) Monomeric ArLi would be Li I (OK), 6-e (not OK). It would probably dimerize via bridging (3c-2e) aryl groups, after which the molecule would be coordinative saturated. Dimerization would also allow formation of a near-tetrahedral (instead of planar) Li environment. N N Li N N Li
g) ArLi would do the normal addition of polar organometallics to carbonyl groups. The expected product after hydrolysis is the alcohol (Ar)(C 6 H 5 )(CH 3 )COH. Side products could be: (1) the starting ketone (ArLi acts as a base, deprotonates the ketone to the enolate, and after hydrolysis the ketone is re-formed), and (2) Ar-Ar and/or [(C 6 H 5 )(CH 3 )COH] 2 (radical coupling, if radicals would be involved in the addition). The latter possibility if not very likely since the ketone does not have a very extended -system. The Sn-C bond is much less polar than the Li-C bond, and the tin compound is also coordinatively (over)saturated, so you expect a low reactivity. Probably, nothing will happen. Treatment with acid might replace he acetate by the anion of the acid used, and acid might also protonate the Me 2 N groups.