1. Actinide Metal Atom (Th and U) Reactions to Form Novel Molecules Metal-Carbon Multiple Bonds Actinide Metal Hydrides Lester Andrews, Chemistry Department, University of Virginia, Charlottesville, Virginia Also Jon Lyon, Han-Gook Cho, Xuefeng Wang, Bjorn Roos, Han-shi Hu, Jun Li, Colin Marsden, Laura Gagliardi

2. Apparatus for Laser Ablation and Matrix Isolation CsI window for IR

3. YAG laser ablation of Zr

5. Novel Organometallic Molecules M + CH 4  CH 3 —MH ↔ CH 2 =MH 2 ↔ HC≡MH 3 M + CH 3 X  CH 3 —MX ↔ CH 2 =MHX ↔ HC≡MH 2 X M + CH 2 X 2  CH 2 X—MX  CH 2 =MX 2  HC≡MHX 2 M + CHX 3  CHX 2 —MX  CHX=MX 2  HC≡MX 3 M + CX 4  CX 3 —MX  CX 2 =MX 2  XC≡MX 3

6. B3LYP density functional calculated structures for methylidene molecules

7. Infrared spectra of the Th + CH 4 reaction product J. Phys. Chem. A 2005, 105, 6796. Dep at 7 K 240-380 nm > 220 nm Anneal 26 K > 420 nm

8. Observed and Calculated (B3LYP/6-311++G(3df,3pd)/SDD) Frequencies for CH 2 =ThH 2 Approximate Mode Description CH 2 =ThH 2 13 CH 2 =ThH 2 CD 2 =ThD 2 Obs.Calc.Int.Obs.Calc.Int.Obs.Calc.Int. CH 2 stretch3142.623132.222321.72 CH 2 stretch2861.4112854.9112084.72 ThH 2 stretch1435.71434.93501435.71434.8350b1023.5110 ThH 2 stretch1397.11394.26981391.71394.2698b1005.798 CH 2 bend1327.5111320.511989.0340 C=Th stretch670.8679.6178651.5659.7173602.9614.8127 CH 2 wag634.6633.0161629.2627.5157499.2495.1109 ThH 2 bend458.7492.8110492.3108355.834 ThH 2 rock460.85458.24344.429 CH 2 twist343.030342.530245.318 ThH 2 wag321.965321.666230.230 CH 2 rock248.462248.162177.530

9. CH 2 =ThH 2, CH 2 =ThHF, CH 2 =UH 2, CH 2 =UHF CH 2 =UHF CH 2 =ThHF

10. Structures calculated with different theoretical methods Inorg. Chem. 2007, 46, 4917. BPW91/PW91/CASPT2

11. One singly-occupied U 5f orbital in CH 2 =UH 2

12. Reactions of laser-ablated U atoms with CH 2 XY (XY = F 2, FCl, and Cl 2 ) lead to a series of new actinide methylidene complexes CH 2 =UF 2, CH 2 =UFCl, and CH 2 =UCl 2, which have agostic structures stabilized by interaction through the open-shell U 6d-5f orbitals. Angew. Chem. Intl. Ed. 2007, 46, 9045.

13. Structures for Th, U and NH 3 Reaction Products Chem. Eur. J. 2007, 13, 5601. B3LYP/CCSD

14. H-N=ThH 2 H-N=UH 2 1.9031.951 62.1% d 30.1% f HOMO 46.2% d 48.5% f HOMO CH 2 =ThH 2 2.103 CH 2 =UH 2 2.045 Small amount of triple bond character

15. Novel Organometallic Molecules M + CH 4  CH 3 —MH ↔ CH 2 =MH 2 ↔ HC≡MH 3 M + CH 3 X  CH 3 —MX ↔ CH 2 =MHX ↔ HC≡MH 2 X M + CH 2 X 2  CH 2 X—MX  CH 2 =MX 2  HC≡MHX 2 M + CHX 3  CHX 2 —MX  CHX=MX 2  HC≡MX 3 M + CX 4  CX 3 —MX  CX 2 =MX 2  XC≡MX 3

16. Th atom reactions with CHF 3, CHF 2 Cl, CHFCl 2, and CHCl 3 CHF 3

17. Approximate HC÷ThF 3 DC÷ThF 3 ModeObs.(argon matrix)B3LYP Calc. (int.)Obs.(argon matrix)B3LYP Calc. (int.) C-H stretch, a 1 3108.6 (5)2288.6 (0) Th-F stretch, a 1 565.4568.5 (17)563.4566.0 (30) Th-F stretch, e521.3526.0 (419)520.6525.7 (404) C-Th stretch, a 1 502.1508.9 (180)493.1492.3 (160) H-C-Th bend, e425.9 (68)328.3 (56) F-Th-F bend, a 1 120.5 (1)117.4 (4) F-Th-F bend, e117.5 (27)115.4 (27) C-Th-F bend, e106.0 (37)102.0 (17) Observed and Calculated Fundamental Frequencies for HC÷ThF 3 in C 3v Symmetry in the Triplet Ground Electronic State Eur. J. Inorg. Chem. 2008, in press.

18. Energies of Th and U atom reactions with CHF 3 and CF 4 2.48 Å 2.16 Å 2.41 Å 2.13 Å 1.94 Å CHF 2 --ThF  CHF=ThF 2  HC—ThF 3 CHF=UF 2  HC≡UF 3 +76 kcal/mol + 46 kcal/mol 0 kcal/mol + 23 kcal/mol 0 kcal/mol 2.26 Å 2.47 Å 2.40 Å CF 2 =ThF 2  CF 2 —ThF 2  FC—ThF 3 + 51 kcal/mol + 51 kcal/mol 0 kcal/mol 2.45 Å 2.40 Å 2.01 Å CF 2 —UF 2  CF 2 =UF 2  FC≡UF 3 + 21 kcal/mol + 20 kcal/mol 0 kcal/mol

19. B3LYP Structures for HC-ThX 3 and XC-ThX 3 Complexes

22. Uranium atom reaction products Proc. Natl. Acad. Sci. 2007, 104, 18919. U+CDF 3 U+CF 4 U + CDF 3 U + CF 4 U + CDF 3 U + CHF 3

23. Observed and calculated (PW91/TZ2P) fundamental vibrational frequencies for the C 3v F 3 U≡CX (X = H, D, F) molecules Mode descriptionF 3 U≡CHF 3 U≡ 13 CHF 3 U≡CDF 3 U≡CF Obs.Calc.Obs.Calc.Obs.Calc.Obs.Calc. C-X str, a 1 2979(0.1)2969(0.2)–2200(1.5)–1268(312) U≡CX str, a 1 –747(46)--721(42)–717(41)–441(34) U-F sym str, a 1 576.2585(122)--585(123)576.2586(123)578.7589(118) U-F antisym str, e540.2561(284)539.2559(280)535.9541(207)536.4544(177) U≡C-X bend, e527.5508(34)--506(24)--412(49)–311(28)

24. Calculated structures of (a) F 3 U≡CH, (b) Cl 3 U≡CH, (d) Br 3 U≡CH, and (d) F 3 U≡CF

25. Comparison of the molecular orbitals of ethyne HC≡CH and the uranium- methylidyne F 3 U≡CH and F 3 U≡CF complexes (isosurface =0.05 atomic unit) HC≡CH F 3 U≡CH F 3 U≡CF π 1 -MO π 2 -MO σ-MO

26. Uranium atom reaction products CHCl 3 13 CHCl 3 CDCl 3 CHBr 3

27. Observed and calculated (PW91/TZ2P) fundamental vibrational frequencies for the C 3v X 3 U≡CH (X = Cl, Br) molecules Mode descriptionCl 3 U≡CHCl 3 U≡ 13 CHCl 3 U≡CDBr 3 U≡CH Obs. b Calc.Obs.Calc.Obs.Calc.Obs.Calc. C-H str, a 1 3001(2)2991(2)2219(7)3005(3) U≡CX str, a 1 –c–c 770(69)–c–c 744(65)–c–c 738(64)–c–c 777(70) U≡C-H bend, e527.2522(224)522.8518(218)415.9410(216)527.6527(178) U-X sym str, a 1 339(29) 225(84) d U-X antisym str, e329(140)– –326(100)216(10) d

28. Carbon-Uranium Triple Bonds 1.764 Å 1.808 Å 1.910 Å C≡U≡O HC≡UCl 3 PW91 bond lengths Zhou, Andrews, Li, Bursten, Lyon, Hu, Andrews, Li, J. Am. Chem. Soc. 1999, 121, 9712. Proc. Natl. Acad. Sci. U.S. Earlier work: 2007, 104(48), 18919. Tague, Andrews, Hunt, J. Phys. Chem. 1993, 97, 10920. Pyykko, Li, Runeberg, J. Phys. Chem. 1994, 98, 4809.

29. Reactions of Mo atoms with CHX 3 molecules: HC ≡ MoX 3

30. Reactions of Mo atoms with CHX 3 molecules Organometallics, 2007, 26, 6373. CHF 3 CHF 2 Cl CHFCl 2 CHCl 3 Natural Mo isotopic splittings

31. Approximate Description HC ≡ MoCl 3 DC ≡ MoCl 3 HC ≡ MoF 3 obscalcint obs calcint obs calcint C-H str, a 1 3058.23212.2352296.2 2387.9243073.1 3221.239 HC ≡ Mo str, a 1 978.1 b 1051.98932.4 b 1005.86986.0 c 1065.020 Mo-X str, e438.7425.081x2436.4 423.074x2689.2 683.4210x2 Mo-X str, a 1 380.89 380.79664.6 651.760 H-C-Mo def, e658.9660.276x2533.4 533.652x2645.4 642.730x2 C-Mo-X def, e237.77x2 212.37x2 288.75x2 Mo-X 3 umb, a 1 144.00 143.70 228.09 Mo-X 2 bend, e100.40 0 163.68x2 Observed and Calculated [B3LYP/6-311++G(2d,p) ] Fundamental Frequencies of HC≡MoX 3 Complexes in the Ground 1 A 1 Electronic State with the C 3v Structure

32. Span the periodic table U + H 2

33. U in solid para-hydrogen at 4 K J. Phys. Chem. A, 2007, 111, 6383.

34. Th in solid H 2, HD, and D 2 at 4 K J. Phys. Chem. A, 2008, in press.

35. Ground state total CASSCF electron density WH 4 (triplet) ThH 4 (singlet) UH 4 (triplet) WH 4 4H 2 (singlet) ThH 4 4H 2 (singlet) UH 4 6H 2 (triplet)

36. Ball Game!!! We have investigated reactions of the laser- ablated actinide metal atoms Th and U with small molecules, and assigned the new reaction products from matrix infrared spectra and comparison with DFT calculated isotopic frequencies. These new molecules are important for their unique bonding and structure and their unusual chemistry. We thank NSF for support and you for your kind attention.

37. Matrix-Isolation Spectroscopy Synthesis Gas-Phase Theory PERSPECTIVE