UVvis Spectroscopy Electronic Spectroscopy What does it monitor

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UV/vis Spectroscopy = Electronic Spectroscopy What does it monitor / probe? What information about

UV/vis Spectroscopy = Electronic Spectroscopy What does it monitor / probe? What information about molecule can one obtain?

1 H NMR: what do you expect to see?

1 H NMR: what do you expect to see?

a a b b c c Expected: 3 resonances, 2 -CH 3 (a &

a a b b c c Expected: 3 resonances, 2 -CH 3 (a & c with 6 H) and 1 H (b) ( B-H not visible due to broadening) … plus H’s on cation TEA = [N(CH 2 CH 3)4]+

1 H NMR: what do you expect to see? [Tp*Mo(S)(S 4)]—

1 H NMR: what do you expect to see? [Tp*Mo(S)(S 4)]—

d e f Mo=S Mo=O a b c a TEA+ b c -CH 3

d e f Mo=S Mo=O a b c a TEA+ b c -CH 3 TEA+ -CH 2 - a b e c f d

d e f Mo=S Mo=O a b c a TEA+ b c -CH 3

d e f Mo=S Mo=O a b c a TEA+ b c -CH 3 TEA+ -CH 2 - a b e c f d

R 1 ≠ R 2: How many H’s expected in NMR from pyrazole rings?

R 1 ≠ R 2: How many H’s expected in NMR from pyrazole rings? All -methyl and ring H’s will be unique: see 6 -Me and 3 ring H

Mass Spectometry Facility Dr. Arpad Somogyi

Mass Spectometry Facility Dr. Arpad Somogyi

Electrospray Ionization Mass Spectrometry ESI-MS black box Molecules in gas phase as ions +

Electrospray Ionization Mass Spectrometry ESI-MS black box Molecules in gas phase as ions + or - magnetic field separates light and heavy mass ions mass detector

Electron impact ionization

Electron impact ionization

Electrospray ionization method makes tiny droplets Vacuum removes solvent Electric potential creates + and

Electrospray ionization method makes tiny droplets Vacuum removes solvent Electric potential creates + and - ions

All Mo molecules are identified by a characteristic series of lines: Mo isotopes: 92

All Mo molecules are identified by a characteristic series of lines: Mo isotopes: 92 Mo, 94 Mo, 95 Mo, 96 Mo, 97 Mo, 98 Mo,

YELLOW (calculated mass spectrum) Mass 474. 000 476. 000 477. 000 478. 000 479.

YELLOW (calculated mass spectrum) Mass 474. 000 476. 000 477. 000 478. 000 479. 000 480. 000 482. 000 481. 000 484. 000 483. 000 486. 000 485. 000 488. 000 475. 000 487. 000 489. 000 490. 000 Relative abundance 6. 12 8. 84 7. 34 11. 91 10. 57 17. 08 14. 14 7. 06 6. 00 3. 06 1. 29 0. 94 0. 14 0. 88 0. 18 0. 02 0. 01

RED (calculated mass spectrum) Mass 404. 000 406. 000 407. 000 408. 000 409.

RED (calculated mass spectrum) Mass 404. 000 406. 000 407. 000 408. 000 409. 000 410. 000 412. 000 411. 000 414. 000 405. 000 413. 000 415. 000 416. 000 417. 000 418. 000 Relative abundance 11. 48 8. 72 12. 64 15. 04 10. 98 20. 73 10. 58 4. 24 1. 58 1. 66 1. 55 0. 21 0. 10 0. 01 0. 00

BLUE (calculated mass spectrum) Mass 468. 000 470. 000 471. 000 472. 000 473.

BLUE (calculated mass spectrum) Mass 468. 000 470. 000 471. 000 472. 000 473. 000 474. 000 476. 000 475. 000 478. 000 469. 000 477. 000 479. 000 480. 000 481. 000 482. 000 483. 000 Relative abundance 10. 36 8. 81 11. 67 14. 47 11. 15 20. 10 11. 30 5. 04 2. 33 1. 66 1. 93 0. 35 0. 24 0. 03 0. 01 0. 00

PURPLE (calculated mass spectrum) Mass 824. 000 826. 000 827. 000 828. 000 829.

PURPLE (calculated mass spectrum) Mass 824. 000 826. 000 827. 000 828. 000 829. 000 830. 000 832. 000 831. 000 834. 000 833. 000 835. 000 836. 000 837. 000 838. 000 840. 000 839. 000 842. 000 841. 000 844. 000 Relative abundance 1. 32 2. 03 3. 18 4. 63 5. 22 9. 33 11. 22 7. 37 10. 77 9. 98 8. 87 9. 11 5. 00 5. 46 1. 99 0. 43 0. 58 0. 06

Y R P B All have one Mo atom More lines, more Mo atoms

Y R P B All have one Mo atom More lines, more Mo atoms

RED mass spectrum 409. 6

RED mass spectrum 409. 6

YELLOW mass spectrum 444. 6

YELLOW mass spectrum 444. 6

BLUE full mass spectrum

BLUE full mass spectrum

YELLOW (high mass species)

YELLOW (high mass species)

Accurate mass : 540. 019287 for Modetc 3 Mass 536. 000 538. 000 539.

Accurate mass : 540. 019287 for Modetc 3 Mass 536. 000 538. 000 539. 000 540. 000 541. 000 542. 000 544. 000 537. 000 543. 000 545. 000 546. 000 547. 000 548. 000 549. 000 550. 000 551. 000 Relative abundance 9. 82 8. 43 11. 53 14. 33 11. 33 19. 63 10. 96 2. 13 5. 83 2. 42 2. 30 0. 45 0. 25 0. 04 0. 02 0. 00 Accurate mass : 556. 014160 for Mo. Odetc 3 Mass 552. 000 554. 000 555. 000 556. 000 557. 000 558. 000 560. 000 559. 000 562. 000 553. 000 561. 000 563. 000 564. 000 565. 000 566. 000 567. 000 Relative abundance 9. 80 8. 44 11. 51 14. 32 11. 33 19. 62 10. 98 5. 85 2. 32 2. 12 2. 43 0. 46 0. 25 0. 04 0. 02 0. 00

Mo. Odetc 2: Mo 1 S 4 O 1 N 2 C 10 H

Mo. Odetc 2: Mo 1 S 4 O 1 N 2 C 10 H 20 mass: 408. 48 g/mol Mo. Odetc 2. NCCH 3: Mo 1 S 4 O 1 N 3 C 12 H 23 mass: 449. 53 g/mol Mo. OCl 2 detc 2: Mo. Cl 2 S 4 O 1 N 2 C 10 H 20 mass: 479. 38 g/mol Mo 2 O 3 detc 4: Mo 2 S 8 O 3 N 4 C 20 H 40 mass: 832. 96 g/mol Mo. OS 2 detc 2: Mo. S 6 ON 2 C 10 H 20 mass: 472. 61 g/mol

Mo. OCl 2 detc 2: Mo. Cl 2 S 4 O 1 N 2

Mo. OCl 2 detc 2: Mo. Cl 2 S 4 O 1 N 2 C 10 H 20 Accurate mass : 478. 893738 Mass 474. 000 476. 000 477. 000 478. 000 479. 000 480. 000 482. 000 481. 000 484. 000 483. 000 486. 000 485. 000 488. 000 475. 000 487. 000 489. 000 490. 000 Relative abundance 6. 12 8. 84 7. 34 11. 91 10. 57 17. 08 14. 14 7. 06 6. 00 3. 06 1. 29 0. 94 0. 14 0. 88 0. 18 0. 02 0. 01

Mo. Odetc 2: Mo 1 S 4 O 1 N 2 C 10 H

Mo. Odetc 2: Mo 1 S 4 O 1 N 2 C 10 H 20 Accurate mass : 407. 987732 Mass 404. 000 406. 000 407. 000 408. 000 409. 000 410. 000 412. 000 411. 000 414. 000 405. 000 413. 000 415. 000 416. 000 417. 000 418. 000 Relative abundance 11. 48 8. 72 12. 64 15. 04 10. 98 20. 73 10. 58 4. 24 1. 58 1. 66 1. 55 0. 21 0. 10 0. 01 0. 00

Mo 2 O 3 detc 4: Mo 2 S 8 O 3 N 4

Mo 2 O 3 detc 4: Mo 2 S 8 O 3 N 4 C 20 H 40 Accurate mass : 831. 970276 Mass 824. 000 826. 000 827. 000 828. 000 829. 000 830. 000 832. 000 831. 000 834. 000 833. 000 835. 000 836. 000 837. 000 838. 000 840. 000 839. 000 842. 000 841. 000 Relative abundance 1. 32 2. 03 3. 18 4. 63 5. 22 9. 33 11. 22 7. 37 10. 77 9. 98 8. 87 9. 11 5. 00 5. 46 1. 99 0. 43 0. 58

Mo. OS 2 detc 2: Mo. S 6 ON 2 C 10 H 20

Mo. OS 2 detc 2: Mo. S 6 ON 2 C 10 H 20 Accurate mass : 471. 931763 Mass 468. 000 470. 000 471. 000 472. 000 473. 000 474. 000 476. 000 475. 000 478. 000 469. 000 477. 000 479. 000 480. 000 481. 000 482. 000 483. 000 Relative abundance 10. 36 8. 81 11. 67 14. 47 11. 15 20. 10 11. 30 5. 04 2. 33 1. 66 1. 93 0. 35 0. 24 0. 03 0. 01 0. 00