32 Covalent radii for sulphur and oxygen are 1.05(3) and 0.66(2) Å, respect-
ively: B. Cordero, V. Gómez, A. E. Platero-Prats, M. Revés,
J. Echeverría, E. Cremades, F. Barragán and S. Alvarez, Dalton Trans.,
2008, 2832.
57 (a) A. J. Bridgeman, G. Cavigliasso, L. R. Ireland and J. Rothery, J.
Chem. Soc., Dalton Trans., 2001, 2095; (b) I. Mayer, Chem. Phys. Lett.,
1983, 97, 270. Addendum 1985, 117, 396 (c) I. Mayer, Int. J. Quantum
Chem., 1986, 29, 73; (d) A. B. Sannigrahi and T. Kar, Chem. Phys. Lett.,
1990, 173, 569.
58 (a) R. S. Mulliken, J. Chem. Phys., 1955, 23, 1833; (b) T. A. Albright, J.
K. Burdett and M. H. Whangbo, Orbital Interactions in Chemistry, John
Wiley & Sons, 1985.
33 1H NMR spectra of complexes 3 and 4 in C6D6 were also consistent with
C2v and Cs symmetry, respectively.
34 For advantages of the [NBu4][B(C6F5)4] anion as the base electrolyte in
transition metal electrochemistry, see:
(a) N. C. Ohrenberg, L.
M. Paradee, R. J. DeWitte, D. S. Chong and W. E. Geiger, Organometal-
lics, 2010, 29, 3179; (b) J. C. Swarts, A. Nafady, J. H. Roudebush,
S. Trupia and W. E. Geiger, Inorg. Chem., 2009, 48, 2156; (c) D.
S. Chong, J. Slote and W. E. Geiger, J. Electroanal. Chem., 2009, 630,
28; (d) A. Nafady and W. E. Geiger, Organometallics, 2008, 27, 5624;
(e) D. Chong, D. R. Laws, A. Nafady, P. J. Costa, A. L. Rheingold, M.
J. Calhorda and W. E. Geiger, J. Am. Chem. Soc., 2008, 130, 2692;
(f) A. Nafady, T. T. Chin and W. E. Geiger, Organometallics, 2006, 25,
1654; (g) F. Barrière, R. U. Kirss and W. E. Geiger, Organometallics,
2005, 24, 48; (h) N. Camire, A. Nafady and W. E. Geiger, J. Am. Chem.
Soc., 2002, 124, 7260; (i) N. Camire, U. T. Mueller-Westerhoff and W.
E. Geiger, J. Organomet. Chem., 2001, 637, 823; ( j) Ref. 72 (k) Ref. 74.
59 (a) F. L. Hirshfeld, Theor. Chim. Acta, 1977, 44, 129; (b) E. R. Davidson
and S. Chakravorty, Theor. Chim. Acta, 1992, 83, 319; (c) C. F. Guerra, J.
W. Handgraaf, E. J. Baerends and F. M. Bickelhaupt, J. Comput. Chem.,
2004, 25, 189; (d) S. Saha, R. K. Roy and P. W. Ayers, Int. J. Quantum
Chem., 2009, 109, 1790; (e) K. B. Wiberg and P. R. Rablen, J. Comput.
Chem., 1993, 14, 1504.
60 R. F. Bader, Atoms in Molecules: A Quantum Theory, Clarendon,
New York, 1990.
61 C. F. Matta and R. J. Boyd, The Quantum Theory of Atoms in Molecules,
Wiley-VCH, Weinheim, 2007.
62 (a) P. L. Arnold, Z. R. Turner, N. Kaltsoyannis, P. Pelekanaki, R.
M. Bellabarba and R. P. Tooze, Chem.–Eur. J., 2010, 16, 9623; (b) M.
J. Tassell and N. Kaltsoyannis, Dalton Trans., 2010, 39, 6719;
(c) I. Kirker and N. Kaltsoyannis, Dalton Trans., 2011, 40, 124.
63 B. Vlaisavljevich, P. Miró, C. J. Cramer, L. Gagliardi, I. Infante and S.
T. Liddle, Chem.–Eur. J., 2011, 17, 8424.
64 E. Di Santo, M. del C. Michelini and N. Russo, Organometallics, 2009,
28, 3716.
65 A. E. Clark, J. L. Sonnenberg, P. J. Hay and R. L. Martin, J. Chem.
Phys., 2004, 121, 2563.
i
35 For examples of the use of the [NR4][B(C6F5)4] (R = nBu or Pr) base
electrolytes in actinide electrochemistry, see: (a) R. K. Thomson, B.
L. Scott, D. E. Morris and J. L. Kiplinger, C. R. Chim., 2010, 13, 790
and refs therein; (b) E. J. Schelter, R. L. Wu, B. L. Scott, J.
D. Thompson, T. Cantat, K. D. John, E. R. Batista, D. E. Morris and J.
L. Kiplinger, Inorg. Chem., 2010, 49, 924; (c) Ref. 9 (d) Ref. 38 (e) Ref.
50.
36 We were unable to obtain cyclic voltammograms for uranium(III) com-
plexes 5 and 6, perhaps due to rapid reaction with the 100-fold excess of
[NBu4][B(C6F5)4] base electrolyte.
66 L. J. Farrugia, P. R. Mallinson and B. Stewart, Acta Crystallogr., Sect. B:
Struct. Sci., 2003, 59, 234.
37 The CVof complex 3 was also unchanged after addition of 10 equivalents
of [NBu4]Cl.
38 D. E. Morris, R. E. Da Re, K. C. Jantunen, I. Castro-Rodriguez and J.
L. Kiplinger, Organometallics, 2004, 23, 5142.
39 C. A. Cruz, T. Chu, D. J. H. Emslie, H. A. Jenkins, L. E. Harrington and
J. F. Britten, J. Organomet. Chem., 2010, 695, 2798.
40 J. Maynadié, J. C. Berthet, P. Thuéry and M. Ephritikhine, Organometal-
lics, 2007, 26, 4585.
41 J. Brennan, R. Shinomoto, A. Zalkin and N. Edelstein, Inorg. Chem.,
1984, 23, 4143.
42 M. Roger, T. Arliguie, P. Thuéry and M. Ephritikhine, Inorg. Chem.,
2008, 47, 3863.
67 P. Macchi and A. Sironi, Coord. Chem. Rev., 2003, 238, 383.
68 (a) D. Stalke, Chem.–Eur. J., 2011, 17, 9264; (b) F. Fuster and S.
J. Grabowski, J. Phys. Chem. A, 2011, 115, 10078.
69 Bond critical point elipticity values (εb; a measure of the extent to which
electron density is preferentially accumulated in a given plane containing
the bond path; 0.00 in ethane and acetylene, 0.23 in benzene and 0.45 in
ethylene) are often not meaningful for very polar bonds, and as a result,
the εb values in Table 3 do not follow any clear trend. See ref. 61 and
68a.
70 (a) D. Cremer and E. Kraka, Croat. Chim. Acta, 1984, 57, 1259;
(b) D. Cremer and E. Kraka, Angew. Chem., Int. Ed. Engl., 1984, 23,
627.
43 W. J. Evans, T. J. Boyle and J. W. Ziller, Inorg. Chem., 1992, 31, 1120.
44 D. J. Mihalcik, J. L. White, J. M. Tanski, L. N. Zakharov, G. P. A. Yap,
C. D. Incarvito, A. L. Rheingold and D. Rabinovich, Dalton Trans.,
2004, 1626.
71 J. L. Kiplinger, D. E. Morris, B. L. Scott and C. J. Burns, Organometal-
lics, 2002, 21, 5978.
72 R. J. LeSuer, C. Buttolph and W. E. Geiger, Anal. Chem., 2004, 76,
6395.
45 (a) B. Martín-Vaca, A. Dumitrescu, H. Gornitzka, D. Bourissou and
G. Bertrand, J. Organomet. Chem., 2003, 682, 263; (b) H.-X. Li, Q.-
F. Xu, J.-X. Chen, M.-L. Cheng, Y. Zhang, W.-H. Zhang, J.-P. Lang and
Q. Shen, J. Organomet. Chem., 2004, 689, 3438; (c) H.-X. Li, Z.-
G. Ren, Y. Zhang, W.-H. Zhang, J.-P. Lang and Q. Shen, J. Am. Chem.
Soc., 2005, 127, 1122.
46 (a) P. C. Blake, E. Hey, M. F. Lappert, J. L. Atwood and H. Zhang,
J. Organomet. Chem., 1988, 353, 307; (b) P. C. Blake, M. F. Lappert,
J. L. Atwood and H. Zhang, J. Chem. Soc., Chem. Commun., 1988,
1436.
73 P. v. D. Sluis and A. L. Spek, Acta Crystallogr., Sect. A: Found. Crystal-
logr., 1990, 46, 194.
74 F. Barrière and W. E. Geiger, J. Am. Chem. Soc., 2006, 128, 3980.
75 (a) ADF2010, SCM, Theoretical Chemistry, Vrije Universiteit, Amster-
dam, The Netherlands, http://www.scm.com/; (b) G. te Velde, F.
M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E.
J. Baerends, J. G. Snijders and T. Ziegler, J. Comput. Chem., 2001, 22,
931; (c) C. Fonseca Guerra, J. G. Snijders, G. te Velde and E.
J. Baerends, Theor. Chem. Acc., 1998, 99, 391.
76 (a) S. J. A. van Gisbergen, J. G. Snijders and E. J. Baerends, Phys. Rev.
Lett., 1997, 78, 3097; (b) S. J. A. van Gisbergen, J. G. Snijders and E.
J. Baerends, J. Chem. Phys., 1998, 109, 10644.
47 In uranium(III) complex 5, some U–S bonding contribution arising from
diarylthioether π-acidity cannot be excluded:
(a) H.-B. Kraatz,
H. Jacobsen, T. Ziegler and P. M. Boorman, Organometallics, 1993, 12,
76; (b) G. E. D. Mullen, M. J. Went, S. Wocadlo, A. K. Powell and P.
J. Blower, Angew. Chem., Int. Ed. Engl., 1997, 36, 1205.
48 I. Korobkov, S. Gambarotta and G. P. A. Yap, Organometallics, 2001, 20,
2552.
49 D. Cohen and W. T. Carnall, J. Phys. Chem., 1960, 64, 1933.
50 E. J. Schelter, P. Yang, B. L. Scott, J. D. Thompson, R. L. Martin, P.
J. Hay, D. E. Morris and J. L. Kiplinger, Inorg. Chem., 2007, 46, 7477.
51 M. J. Monreal, C. T. Carver and P. L. Diaconescu, Inorg. Chem., 2007,
46, 7226.
52 H. Nakai, X. L. Hu, L. N. Zakharov, A. L. Rheingold and K. Meyer,
Inorg. Chem., 2004, 43, 855.
53 A. E. Enriquez, B. L. Scott and M. P. Neu, Inorg. Chem., 2005, 44, 7403.
54 E. Zych and J. Drożdżyński, J. Less Common Met., 1990, 161, 233.
55 L. R. Avens, S. G. Bott, D. L. Clark, A. P. Sattelberger, J. G. Watkin and
B. D. Zwick, Inorg. Chem., 1994, 33, 2248.
77 S. H. Vosko, L. Wilk and M. Nusair, Can. J. Phys., 1980, 58, 1200.
78 (a) E. van Lenthe, E. J. Baerends and J. G. Snijders, J. Chem. Phys.,
1993, 99, 4597; (b) E. van Lenthe, E. J. Baerends and J. G. Snijders,
J. Chem. Phys., 1994, 101, 9783; (c) E. van Lenthe, A. Ehlers and
E.-J. Baerends, J. Chem. Phys., 1999, 110, 8943; (d) E. van Lenthe, J.
G. Snijders and E. J. Baerends, J. Chem. Phys., 1996, 105, 6505;
(e) E. van Lenthe, R. van Leeuwen, E. J. Baerends and J. G. Snijders,
Int. J. Quantum Chem., 1996, 57, 281.
79 (a) J. P. Perdew, Phys. Rev. B, 1986, 33, 8822; (b) J. P. Perdew and
Y. Wang, Phys. Rev. B: Condens. Matter, 1992, 45, 13244.
80 (a) S. I. Gorelsky and A. B. P. Lever, J. Organomet. Chem., 2001, 635,
187; (b) AOMix: Program for Molecular Orbital Analysis, http://www.sg-
chem.net/, University of Ottawa, version 6.4, 2010.
81 T. A. Keith, AIMAll (Version 10.12.13), 2010 (http://aim.tkgristmill.com/).
82 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb,
J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson,
H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov,
56 X. Hu and W. Yang, J. Chem. Phys., 2010, 132, 054109.
8188 | Dalton Trans., 2012, 41, 8175–8189
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