® CH 431-3" MIDTERM HOMEWORK FALL 2002 ANSWER REY R.A. ones L. Draw the catalytic cycle for the hydrogenation of an alkene using W itkinsoii's catalyst. Give the oxidation state and eleotron count for the metal at each step. Clive the type of reaction for each step (e.g. insertion. oxidative addition. ete) 8 e ADo4 4 PPL Arcee, 4 RuCl (Phy), i“ Few a 41, bem ) = Phy lf ‘ Adotos &% i MPA eX. Ab0, 43,16 43, \Fe™ POH TaAsrer # ok Alhene Phy? S PPT . taser has Bere — 7 Fh te BR, Phe = RywCOM, hye d i tt ite” REDUCT WR . Ee. £3, Ge" 2. If you wanted to produce polyethylene by creating an active catalyst system fom Cp22rCh plus "MAO" which solvent would you cho FLELE? (circle correct answer). What is the form of the the catalytically active Sp8tI& which is generated by the interaction of these two components? —ne[® {ene 3. Name four industrial reactions which make use of homogeneous catalysis. Pick 4: A ORAGEWATION On DATION PoEYMERLZATION OUI GOMERI ZA TION OXY CHLORINATION Efomdaten HY DRoFORMYLATION HYDROCYAN ATION OLEFIN METATHESIS4, Which of the following compounds has the most kinetically stable metal carbon bonds ‘and why? be snr ete (PPha)sP-(CHa-CHy)e, (Pha) PE(CHy SiMes, (PPPs )PtCl: A ae yee 4 Bou, THs OwE, 17 HAS No BOHN Moles Te UmdERGo B-W Coimishten 5. How can [tell the difference between oxidative addition and migratory insertion reactions based on knowledge of oxidation state formalism ~ Give an example of each to illustrate your answer. OX, ADD — CWE wl OKDATION STATE - often BY 2 UMTS INSERTIONS - NO CHAE IN Om OATOM STATE 6, (Mim) When the strong Lewis acid B(CsFs)s reacts with CpZrMe; an olefin Polymerization catalyst system is generated. Explain how this happens BUA, aasmers HE eto Ze Te etm [gee] g ety + 6(06), ~ G rene|® Pree leadyl? 7. (10 pis) Assign the tacticity of the polypropylene produced when each of the following metallocenes is activated for olefin polymerization (a) CpiZrCle ZCly SB AS) {b)8, (Mga) Explain how 1, 7 octadiene (CH: = CH — (CH:),-CH = CHa) can be converted in the polymer = (CH), ~(- CH = CH = (CHa).-)- CH = CH - by using olefin metatheis reactions =F Rint Cesta mearnesie (Ro) ? © Me > era), ~[- 82a (14), -) a 2c = 9, Give examples of the following types of reaction + Oe (4, Rial of vw METATHECT PU%ASILAT om (Rome) {2) oxidative addition (b) reductive elimination () insertion ) oxdahie adds, hs rT Hy etn eq. Ir —_ _ 4 ot” \pPk ao” 1 ha 3 hy ¥) reduchie eliminate KR h e My Po Vs mHe Phyto * . — NR ay sa yee “Seay rst FPP Poe4 lad <) tater hens ° Ge) eMart) Feo —> (o)y A= e-city Ti(wite,)g + T (Rema) a, 10. What process is generally responsible for the kinetic instability of many transition metal c-bonded alkyls? How can this process be prevented. Give examples Bo Hysdroman “elas cnahin’ on “ab teachin” 4 HR < ” 44 Ne ~> “de componitan u upon Hy The pon can be preveded by the me of Inganes whith “hee ne fr bydeyen ale (25 cy, CH, Ae HCH Siete 65. THe, (cH, Sittey)g ae M=CHy-ca-R _ 11, What is a Ziegler-Natta catalyst and what is it used for? a “gle Naty ca tt? a hateragasean Papentin . a en solahan of Ti (by tk the preeace + Friaihylaham inven The ache speués prdaceA a tibroy tome of Ck, The cobalyet m med be poymeric alkenes (ek lene p a) (ere retin, mebthnene bast eee sp re ea wat on GA Me, (me Ti &, Hh) ,® Metal carbon double bonds (M=CRz) are described as either an alkylidene or a carbene. plain the differences as fully as possible, giving examples. ‘ hd al 0x. 5kR mek Hee e's Ta (ACME), — allyl dene bag ox. 5A we 1 Aaleaplic > che Pont @ Gacy ~ carbene Tow 0x. Stk vat ok se Eledrop hibit «-Corhan Stem , 12, Metal carbon double bonds (M=CR,) are described as either an alkylidene or a carbene, Explain the differences as fully as possible. giving examples. (@)_ the hydroformylation of an alkene using RaCl)(CO}PPh3)s 13, Draw a reaction schemes for the following catalytic eyeles: SEE You mnes {b) the isomerization of an alkene using a transition metal catalyst 14. It is known that Witkinson’s catalyst is active for the hydrogenation of alkenes under mild conditions (Reaction 0) RACIPPh;)s ( RCH=CH,+H, > R-CH,-CH, ‘Draw a mechanistn for the possible reaction of an alkene with ammonia using RhCKPPhs); asa catalysts to produce a primary amine (Reaction I). Suggest reosons ‘why this second catalytic reaction does not work in practice RhCIPPhy)s (I) RCH =CH, +NH, R-CHy-NHz VLE PP, S* solvent bt s SRT ~ Shen? ee ae * S ‘ ROHAN 4 . oRAT a . a ba tog oN aN 1% CHR sAm cake : Te Fen,