4 - h) [M(CO) 4 I(dppe)]-(dppe =...

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1 Chemistry 172 Problem Set #4 Spring 2009 1 . Amides (NR 2 - ) are nitrogen analogues of phosphides (PR 2 - ). a) Describe the expected geometry around nitrogen in each of the following 18e complexes: ( η 3 -allyl)Ru(CO) 2 (NMe 2 ) and ( η 5 -Cp)Ru(CO) 2 (NMe 2 ). Justify your answer. b) Which compound is expected to possess the shorter Ru-N bond? Explain. 2. For the following complexes, draw the most likely geometry, indicate the coordination environment at Ni, give the d electron count and the number of unpaired electrons: a) [Ni(en) 3 ] 2+ ; b) [NiCl 4 ] 2- ; c) [Ni(CN) 4 ] 2- . 3 . On the basis of the 18 electron rule, identify the first-row transition metal for each of the following: a) [M(CO) 7 ] + ; b) H 3 CM(CO) 5 ; c) M(CO) 2 (CS)(PPh 3 )Br; d) [( η 3 -C 3 H 5 )( η 5 -C 5 H 5 )M(CO)] - ; e) (OC) 5 M=C(OCH 3 )(C 6 H 5 ); f) [( η 4 -C 4 H 4 )( η 5 -C 5 H 5 )M] + ; g) ( η 3 -C 3 H 5 )( η 5 -C 5 H 5 )M(CH 3 )(NO) (contains linear NO, nitrosyl);
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Unformatted text preview: h) [M(CO) 4 I(dppe)]-(dppe = 1,2-bis(diphenylphosphino)ethane). 4 . Determine the metal-metal bond order consistent with an 18 electron count for the following: a) [( 5-Cp)Fe(CO) 2 ] 2 ; b) [( 5-Cp)Mo(CO) 2 ] 2 2-5 . On the basis of the 18 electron rule, determine the expected charge on the following: a) [Co(CO) 3 ] z ; b) [Ni(CO) 3 (NO)] z (contains linear NO); c) [Ru(CO) 4 (CMe 3 )] z ; d) ( 3-C 3 H 5 )V(CNCH 3 ) 5 ] z ; e) [( 5-Cp)Fe(CO) 3 ] z ; f) [( 5-Cp) 3 Ni 3 ( 3-CO) 2 ] z 6 . Propose synthetic routes for the following: Pt Cl H 3 N Cl Cl Pt Br H 3 N py Cl Pt Cl Cl Cl Cl Pt Cl O 2 N Cl py 2-a) b) 7 . Account for the observation that two separate water exchange rates are found for [Cu(OH 2 ) 6 ] 2+ in solution....
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