, At least 40 excited states were calculated in each case, 604 and difference transition density plots were generated for each 605 transition. For each transition, difference density plots were generated 606 using the ORCA plot utility program and visualized with the 607 Chemcraft program. The same procedure was also employed to 608 generate and visualize spin-density plots as well as molecular orbitals, the Tamm?Dancoff approximation. 104,105, p.609

, General Procedure for the Synthesis of, Synthetic Procedures

R. Complexes, (. R-=-nme-2, H. , and C. , Br). previously cooled to ?30°C resulted in the precipitation of a 617 solid. The solid was isolated, washed with diethyl ether and pentane, 618 and dried in vacuo (yields typically 70?85%), Crystals suitable for X

, CDCl 3 ): ? ppm 1.76 (m, 2H), 2.51 624 (s, 12H), 2.84 (m, 4H), 3.22 (s, 6H), 6.81 (br, 2H), 9.09 (very br, 625 2H). 13 C NMR (125 MHz, CDCl, vol.3, issue.3

, TMPDCu) 2 (?-TfO)(?-? 2 :? 1 -PhNO)](TfO) (3 H ?). Yield: brown solid

H. Nmr, MHz, CDCl, vol.3, issue.500

, CDCl 3 ): ? ppm 22.36, 48.59, 60.59, 120.97 (d upon 15 N 634 labeling, J( 13 C? 15 N) = 3 Hz), 2.69 (br, 8H), 7.49 (t, 2H), 7.67 (t, 1H), 8.09 (d, 2H). 13 C NMR 633 (125 MHz

C. ,

, Yield: prepared in situ 640 (green solution). 1 H NMR (500 MHz, (12H), 2.63 (4H), 7.43 (t, 2H), 7.63 (t, 1H), 7.97 (d, 2H). 13 C 642 NMR (125 MHz, pp.641-643

, CDCl 3 ): not observed. 646 [(TMPDCu)(TfO)(? 2 -p-ClC 6 H 4 NO)](TfO) (3 Cl ). Yield: green solid. 1 H 647 NMR (500 MHz, acetone-d 6 ): ? ppm 2, J( 13 C? 15 N) = 2 Hz), 130.78, 160.67 (d upon 15 N labeling, 645 J( 13 C? 15 N) = 6 Hz). 15 N NMR (50.7 MHz

, Br ). Yield: green solid

H. Nmr, MHz, CDCl, vol.3, issue.500

, br, 4H), 7.54 (d, 2H), 7.91 (d, 1H). 13 C NMR (125 MHz, vol.655

, J( 13 C? 15 N) = 2.5 Hz)

. Hz, CDCl 3 ): not observed. Anal. Calcd for 659 C 14 H, 15 N NMR (50.7 MHz

X. ,

, The Supporting Information is available free of

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