Beruflich Dokumente
Kultur Dokumente
46. T. J. Katz, J. McGinness, J. Am. Chem. Soc., 1975, 97, 57. J. Cossee, J. Catal., 1964, 3, 80; E. J. Arlman, J. Catal.,
1592 and 1977, 99, 1903. 1964, 3, 89; E. J. Arlman, J. Cossee, J. Catal., 1964, 3, 99.
47. A. Fürstner, K. Langemann, J. Org. Chem., 1996, 58. J. J. Eisch, A. M. Piotrowski, S. K. Brownstein, E. J. Gabe,
61, 8746. F. L. Lee, J. Am. Chem. Soc., 1985, 107, 7219.
48. E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc., 59. K. J. Ivin, J. J. Rooney, C. D. Stewart, M. L. H. Green,
1997, 119, 3887. Chem. Commun., 1978, 604.
49. M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. 60. L. Clauson, J. Sato, S. L. Buchwald, M. L. Steigerwald,
Soc. , 2001, 123, 6543. R. H. Grubbs, J. Am. Chem. Soc., 1985, 107, 3377.
50. J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, For a brief review of experiments used to distinguish
Organometallics, 1999, 18, 2370. between the two mechanisms, see G. O. Spessard and
51. L. Ackermann, D. El Tom, A. Fürstner, Tetrahedron, G. L. Miessler, Organometallic Chemistry, Prentice Hall,
2000, 56, 2195. Upper Saddle River, NJ, 1997, pp. 357–369.
52. S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, 61. W. H. Turner, R. R. Schrock, J. Am. Chem. Soc., 1982,
J. Am. Chem. Soc., 2000, 122, 8168. 104, 2331.
53. J. Kress, J. A. Osborn, R. M. E. Greene, K. J. Ivin, 62. E. Fischer, H. Tropsch, Brennst. Chem., 1923, 4, 276.
J. J. Rooney, J. Am. Chem. Soc., 1987, 109, 899. 63. M. M. Taqui Khan, S. B. Halligudi, S. Shukla, Angew.
54. W. A. Nugent and J. M. Mayer, Metal–Ligand Multiple Chem., Int. Ed., 1988, 27, 1735 and R. Ziessel, Angew.
Bonds , Wiley Interscience, New York, 1988, p. 311 and Chem., Int. Ed., 1992, 30, 844.
references therein; U. H. W. Bunz, L. Kloppenburg, 64. J. P. Collins, R. Ruppert, J. P. Sauvage, Nouv. J. Chim.,
Angew. Chem., Int. Ed., 1999, 38, 478. 1985, 9, 395.
55. R. Chang and W. Tikkanen, The Top Fifty Industrial
Chemicals, Random House, New York, 1988; Chem. Eng.
News, July 2, 2011, p. 57.
56. K. Ziegler, E. Holzkamp, H. Breiland, H. Martin, Angew.
Chem., 1955, 67, 541.
General References
J. F. Hartwig, Organotransition Metal Chemistry, From Bonding organometallic reactions, with numerous references to the
to Catalysis, University Science Books, Mill Valley, CA, 2010, original literature. Two recent sources of general information
provides a detailed discussion, with numerous references, of many and recent references on catalytic processes are P. W. N. M.
of the reactions and catalytic processes described in this chapter, van Leeuwen’s, Homogeneous Catalysis: Understanding the Art,
as well as a variety of other types of organometallic reactions. In Kluwer Academic Publishers, Dordrecht, the Netherlands,
addition to providing extensive information on the structural and 2004, and J. Hagen’s Industrial Catalysis: A Practical Approach,
bonding properties of organometallic compounds, G. Wilkinson, 2nd ed., Wiley-VCH, Weinheim, Germany, 2006. S. T. Oyama and
F. G. A. Stone, and E. W. Abel, editors of Comprehensive G. A. Somorjai, “Homogeneous, Heterogeneous, and Enzymatic
Organometallic Chemistry, Pergamon Press, Oxford, UK, 1982, Catalysis” in J. Chem. Educ., 1988, 65, 765, gives examples of
and E. W. Abel, F. G. A. Stone, and G. Wilkinson, editors of the types and amounts of catalysts used in a variety of industrial
Comprehensive Organometallic Chemistry II, Pergamon Press, processes. The references listed at the end of Chapter 13 are also
Oxford, 1995, give the most comprehensive information on useful in connection with this chapter.
Problems
14.1 Predict the transition metal-containing products of the 14.2 Predict the transition metal–containing products of the
following reactions: following reactions:
a. [Mn(CO)5] - + H2C “ CH i CH2Cl h a. H3C i Mn(CO)5 + P(CH3)(C6H5)2 h (no gases
- CO are evolved)
initial product h final product
b. trans@Ir(CO)Cl(PPh3)2 + CH3I h b. [Mn(CO)5] - + (h5@C5H5)Fe(CO)2Br h
c. Ir(PPh3)3Cl h c. trans@Ir(CO)Cl(PPh3)2 + H2 h
d. (h5@C5H5)Fe(CO)2(CH3) + PPh3 h d. W(CO)6 + C6H5Li h
e. (h5@C5H5)Mo(CO)3[C( “ O)CH3] h e. cis@Re(CH3)(PEt3)(CO)4 + 13CO h (show all
f. H3C i Mn(CO)5 + SO 2 h (no gases are expected products, percentage of each)
evolved) f. fac@Mn(CO)3(CH3)(PMe3)2 + 13 CO h (show
all expected products, percentage of each)
Problems | 575
14.3 Predict the transition metal–containing products of the 14.9 The equilibrium constants for the ligand dissociation
following reactions: reaction NiL4 m NiL3 + L have been determined
a. cis@Mn(CO)4(13CO)(COCH3) h (show all for a variety of phosphines. (See C. A. Tolman, W. C.
expected products, percentage of each) Seidel, L. W. Gosser, J. Am. Chem. Soc., 1974, 96, 53).
hv
b. C6H5CH2 i Mn(CO)5 h CO + For L = PMe3, PEt3, PMePh2, and PPh3, arrange these
c. V(CO)6 + NO h equilibria in order of the expected magnitudes of their
d. Cr(CO)6 + Na/NH3 h equilibrium constants (from largest K to smallest).
e. Fe(CO)5 + NaC 5H5 h 14.10 In addition to pioneering the cone angle concept, C. A.
f. [Fe(CO)4]2 - + CH3I h Tolman proposed a parameter x (chi) as a measure of the
g. H3C i Rh(PPh3)3 h CH4 + electronic effect of phosphine and related ligands, based
14.4 Heating [(h5@C5H5)Fe(CO)3] + with NaH in solution on infrared spectra of complexes containing these ligands
gives A, which has the empirical formula C7H6O2Fe . A (C. A. Tolman, J. Am. Chem. Soc., 1970, 92, 2953).
reacts rapidly at room temperature to eliminate a col- a. What was the general formula of the complexes used
orless gas B, forming a purple-brown solid C having by Tolman?
the empirical formula C7H5O2Fe . Treatment of C with b. How was x defined?
iodine generates a brown solid D with the empirical for- c. What types of ligands had high values of x?
mula C7H5O2FeI, which on treatment with TlC5H5 gives d. To what extent does this approach distinguish
a solid E with the formula C12H10O2Fe . E, on heating, between the sigma donor and pi acceptor nature of
gives off a colorless gas, leaving an orange solid F with the ligands studied?
the formula C10H10Fe . Propose structural formulas for A 14.11 The nickel(II) pincer complexes [N(o@C6H4PR2)2]NiX
through F. (1: R = Ph, X = H; 2: R = Ph, X = Me) undergo differ-
14.5 Na[(h5@C5H5)Fe(CO)2] reacts with ClCH2CH2SCH3 to ent reactions with CO on the basis of the R and X groups,
give A, a monomeric and diamagnetic substance of stoi- but the phosphine arms remain attached to the Ni center
chiometry C10H12FeO2S having two strong IR bands at (See L.-C. Liang, Y.-T. Hung, Y.-L. Huang, P.-Y. Lee,
1980 and 1940 cm - 1 . Heating of A gives B, a mono- W.-C. Chen, Organometallics, 2012, 31, 700 for struc-
meric, diamagnetic substance having strong IR bands at tural details of these complexes.)
1920 and 1630 cm - 1. Identify A and B. a. When R = Ph and X = H, the addition of CO results
14.6 The reaction of V(CO)5(NO) with P(OCH3)3 to give in the disappearance of a 1H NMR resonance at
V(CO)4[P(OCH3)3](NO) has the rate law –18 ppm, with the corresponding new signal (that
- d[V(CO)5(NO)] also integrates to one H) at 8.61 ppm. Two y(CO)
= k1 [V(CO)5(NO)] + stretching bands appear in the IR spectrum at 1993
dt
and 1924 cm - 1. Propose a structure for this product
k2[P(OCH3)3][V(CO)5(NO)]
and a mechanism for its formation.
a. Suggest a mechanism for this reaction consistent with
b. When R = Ph and X = Me, the addition of CO results in
the rate law.
the appearance of an intermediate with a single y(CO)
b. One possible mechanism consistent with the last
infrared band at 1621 cm - 1. This intermediate subse-
term in the rate includes a transition state of formula
quently provides another nickel complex with three
V(CO)5[P(OCH3)3](NO). Would this necessarily be
y(CO) infrared bands (2002, 1943, 1695 cm - 1).
a 20-electron species? Explain.
Propose the structures of the intermediate and final
14.7 The rate law for the reaction
product, and the reaction mechanisms involved in
H2 + Co2(CO)8 h 2 HCo(CO)4 is
these reactions.
k[Co2(CO)8][H2] c. Why do the reactions proceed differently when X = H
Rate =
[CO] or X = Me?
Propose a mechanism consistent with this rate law. 14.12 The N,N-dibenzylcyclam ligand supports a novel
14.8 Which of the following trans complexes would you double-cyclometallation reaction of zirconium(IV) (R =
tBu, Me, CH Ph ) in the presence of 4 atm H as depicted
expect to react most rapidly with CO? Which would 2 2
you expect to react least rapidly? Briefly explain your in Scheme 1 of R. F. Munhá, J. Ballmann, L. F. Veiros,
choices. B. O. Patrick, M. D. Fryzuk, Organometallics, 2012,
Cr(CO)4(PPh 3)2 31, 4937.
Cr(CO)4(PPh 3)(PBu3) (Bu = n@butyl) a. Propose a mechanism for this reaction, which pro-
Cr(CO)4(PPh 3)[P(OMe)3] ceeds most slowly for R = CH2Ph , that is consistent
Cr(CO)4(PPh 3)[P(OPh)3] with the rate being independent of H2 pressure.
(See M. J. Wovkulich, J. D. Atwood, Organometallics, b. Explain the reasoning for your selection. Why might
1982, 1, 1316.) the reaction be slowest with R = CH2Ph )?
576 Chapter 14 | Organometallic Reactions and Catalysis
14.13 The complex shown below loses carbon monoxide on 14.18 The carbene complex I shown below undergoes the fol-
heating. Would you expect this carbon monoxide to be lowing reactions. Propose structural formulas for the
12
CO, 13CO, or a mixture of both? Why? reaction products.
O CH3 O
13C
C Br O
O
C
OC Re C
OC Mn PPh3
O
C OC C
O PPh3 O
14.14 a. Predict the products of the following reaction, show- a. When a toluene solution containing I and excess tri-
ing clearly the structure of each: phenylphosphine is heated to reflux, compound II is
formed first, and then compound III. II has infrared
O bands at 2038, 1958, and 1906 cm - 1 and III at 1944
C CH
3 and 1860 cm - 1. 1H NMR data d values (relative area)
OC Mn PMe3 + 13CO are as follows:
II: 7.62, 7.41 multiplets (15)
C PMe3
O 4.19 multiplet (4)
b. Each product of this reaction has a new, rather strong III: 7.70, 7.32 multiplets (15)
IR band that is distinctly different in energy from 3.39 singlet (2)
any bands in the reactants. Account for this band, b. When a solution of I in toluene is heated to reflux
and predict its approximate location (in cm - 1) in the with 1,1-bis(diphenylphosphino)methane, a colorless
IR spectrum. product IV is formed that has the following properties:
14.15 Give structural formulas for A through D: IR: 2036, 1959, 1914 cm - 1
Na/Hg Br2 Elemental analysis (accurate to { 0.3%): 35.87% C,
(h5@C5H5)2Fe2(CO)4 h A h 2.73% H
LiAlH4 PhNa c. I reacts rapidly with the dimethyldithiocarbamate ion
B h C h A + D (a hydrocarbon) S2CN(CH3)2- in solution to form Re(CO)5Br + V,
nCO = 1961, 1942, 1790 cm - 1 for (h5@C5H5)2Fe2(CO)4 a product that does not contain a metal atom. This
product has no infrared bands between 1700 and
A has strong IR bands at 1880 and 1830 cm - 1; C has a 2300 cm - 1. However, it does show moderately
1
H NMR spectrum consisting of two singlets of relative intense bands at 1500 and 977 cm - 1. The 1H NMR
intensity 1:5 at approximately d 912 ppm and d 5 ppm, spectrum of V shows bands at d 3.91 (triplet), 3.60
respectively. (Hint: Metal hydrides often have protons (triplet), 3.57 (singlet), and 3.41 (singlet).
with negative chemical shifts.) (See G. L. Miessler, S. Kim, R. A. Jacobson,
14.16 Re(CO)5Br reacts with the ion Br i CH2 CH 2 i O - to R. J. Angelici, Inorg. Chem., 1987, 26, 1690.)
give compound Y + Br - . 14.19 The complex I in the preceding problem can be
a. What is the most likely site of attack of this ion synthesized from Re(CO)5Br and 2-bromoethanol in
on Re(CO)5Br? (Hint: Consider the hardness (see ethylene oxide solution with solid NaBr present. Suggest
Chapter 6) of the Lewis base.) a mechanism for the formation of the carbene ligand.
b. Using the following information, propose a structural 14.20 BrCH2CH2CH2Mn(CO)5 is formed by reaction of
formula of Y, and account for each of the following: [Mn(CO)5] - with 1,3-dibromopropane. However, the
Y obeys the 18-electron rule. reaction does not stop here; the product reacts with addi-
No gas is evolved in the reaction. tional [Mn(CO)5] - to yield a carbene complex. Propose a
13
C NMR indicates that there are ve distinct mag- structure for this complex, and suggest a mechanism for
netic environments for carbon in Y. its formation.
Addition of a solution of Ag + to a solution of Y gives 14.21 An acyl metal carbonyl (R i C( “ O)M(CO)x) is gener-
a white precipitate. ally easier to protonate than either a metal carbonyl or an
(See M. M. Singh, R. J. Angelici, Inorg. Chem., 1984, organic ketone, such as acetone. Suggest an explanation.
23, 2699.) 14.22 Show how transition-metal complexes could be used to
14.17 What is a nitrenium ligand? How does it compare with an effect the following syntheses:
N-heterocyclic carbene? Which of these types of ligand is a. Acetaldehyde from ethylene
viewed as a stronger sigma donor, and what experimental b. CH3CH2COOCH3 from CH3CH2Cl
evidence supports this view? What role do pincer ligands c. CH3CH2CH2CH2CHO from CH3CH2CH “ CH2
play in nitrenium complexes? (See Y. Tulchinsky, M. A. d. PhCH2CH2CH2CHO from an alkene (Ph = phenyl)
Iron, M. Botoshansky, M. Gandelman, Nature Chem.,
2011, 3, 525.)
Problems | 577
1
IR: strong bands at 1920, 1857 cm - 1 .
1
H NMR: chemical shift (relative area):
5.46 (2)
5.28 (5)
5.15 (3)
4.22 (2)
1.31 (27)
In addition, a small peak is believed to be hidden under
other peaks.