A versatile salt-metathesis route to heteroatomic clusters derived from phosphorus and arsenic Zintl anions

Transcription

1 Supporting Information A versatile salt-metathesis route to heteroatomic clusters derived from phosphorus and arsenic Zintl anions Caroline Knapp, Joseph S. Large, Nicholas H. Rees, Jose M. Goicoechea* Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, OX1 3TA, U.K. Cartesian coordinates [Å] for the optimized structure of [In(P 7 ) 2 ] 3 Atom x y z In P P P P P P P P P P P P P P S1

2 Figure S1. Optimized geometry of the [In(P 7 ) 2 ] 3 cluster anion from DFT calculations. Table S1. Bond distances [Å] and angles [ ] for the [In(P 7 ) 2 ] 3 cluster anion crystallographically characterized in 1 and for the optimized computed structure. Bond [Å] [In(P 7 ) 2 ] 3 [a] [In(P 7 ) 2 ] 3 calc In1-P12, In1-P , , In1-P13, In1-P , , P11-P12, P21-P , , P11-P13, P21-P , , P11-P14, P21-P , , P12-P15, P22-P , , P13-P16, P23-P , , P14-P17, P24-P , , P15-P16, P25-P , , P15-P17, P25-P , , P16-P17, P26-P , , Angle [ ] P12-In1-P P22-In1-P P12-In1-P P12-In1-P P13-In1-P P13-In1-P [a] Mean distances and angles for the two crystallographically unique cluster anions present in the asymmetric unit of 1. S2

3 Cartesian coordinates [Å] for the optimized structure of [TlP 7 ] 2 Atom x y z Tl P P P P P P P Figure S2. Optimized geometry of the [TlP 7 ] 2 cluster anion from DFT calculations. S3

4 Table S2. Bond distances [Å] and angles [ ] for the [TlP 7 ] 2 cluster anion crystallographically characterized in 3 and for the optimized computed structure. Bond [Å] [TlP 7 ] 2 [b] [TlP 7 ] 2 calc Tl1-P Tl1-P Tl1-P Tl1-P P11-P P11-P P11-P P12-P P13-P P14-P P15-P P15-P P16-P Angle [ ] P12-Tl1-P [b] Mean distances and angles for the two crystallographically unique cluster anions present in the asymmetric unit of 3. Cartesian coordinates [Å] for the optimized structure of [TlAs 7 ] 2 Atom x y z Tl As As As As As As As S4

5 Figure S3. Optimized geometry of the [TlAs 7 ] 2 cluster anion from DFT calculations. Table S3. Bond distances [Å] and angles [ ] for the [TlAs 7 ] 2 cluster anion crystallographically characterized in 4b and for the optimized computed structure. Bond [Å] [TlAs 7 ] 2 [TlAs 7 ] 2 calc Tl1-As (2) Tl1-As (1) Tl1-As (2) Tl1-As (2) As11-As (2) As11-As (2) As11-As (2) As12-As (2) As13-As (2) As14-As (2) As15-As (2) As15-As (2) As16-As (2) Angle [ ] As12-Tl1-As (4) S5

6 Figure S4. Thermal ellipsoid plot of the [SnP 15 ] 3 cluster anions present in sample 5. Anisotropic displacement ellipsoids pictured at 50% probability level. If refined as a [P 16 ] 3 anion the final cycle R values are: R1 = and wr2 = for I 2σ(I); R1 = and wr2 = for all the data. Figure S5. Thermal ellipsoid plot of the [PbP 15 ] 3 cluster anions present in sample 6. Anisotropic displacement ellipsoids pictured at 50% probability level. The structure does not refine if the cluster anion is set as [P 16 ] 3. S6

7 Cartesian coordinates [Å] for the optimized structure of [SnP 15 ] 3 Atom x y z Sn As As As As As As As As As As As As As As As Figure S6. Optimized geometry of the [SnAs 15 ] 3 cluster anion from DFT calculations. S7

8 Table S4. Bond distances [Å] and angles [ ] for the [SnAs 15 ] 3 cluster anion crystallographically characterized in 7 and for the optimized computed structure. Bond [Å] [SnAs 15 ] 3 [SnAs 15 ] 3 calc Sn1-As (1) Sn1-As (1) Sn1-As (1) As2-As (1) As9-As (1) As1-As2, As8-As (1), 2.410(1) 2.490, As1-As3, As8-As (1), 2.417(1) 2.471, As1-As4, As8-As (1), 2.370(1) 2.414, As2-As5, As9-As (1), 2.412(1) 2.456, As3-A6, As10-As (1), 2.395(1) 2.439, As4-As7, As11-As (1), 2.384(1) 2.435, As5-As6, As12-As (1), 2.466(1) 2.525, As5-As7, As12-As (1), 2.466(1) 2.513, As6-As7, As13-As (1), 2.458(1) 2.513, Angle [ ] As3-Sn1-As (3) As2-As15-As (3) As3-Sn1-As (2) As10-Sn1-As (2) As2-As15-Sn (3) As9-As15-Sn (3) S8

9 Figure S7. Negative ion mode electrospray mass spectrum of a DMF solution of sample 1. S9

10 Figure S8. Positive ion mode electrospray mass spectrum of a DMF solution of sample 1. S10

11 Figure S9. Negative ion mode electrospray mass spectrum of a DMF solution containing sample 2. S11

12 Figure S10. Positive ion mode electrospray mass spectrum of a DMF solution containing sample 2. S12

13 Figure S11. Negative ion mode electrospray mass spectrum of a DMF solution of sample 3. S13

14 Figure S12. Positive ion mode electrospray mass spectrum of a DMF solution of sample 3. S14

15 Figure S12. Negative ion mode electrospray mass spectrum of a DMF solution of sample 4b. S15

16 Figure S13. Positive ion mode electrospray mass spectrum of a DMF solution of sample 4b. S16

17 Figure S14. Negative ion mode electrospray mass spectrum of a DMF solution containing sample 5. S17

18 Figure S15. Positive ion mode electrospray mass spectrum of a DMF solution containing sample 5. S18

19 Figure S16. Negative ion mode electrospray mass spectrum of a DMF solution containing sample 6. S19

20 Figure S17. Positive ion mode electrospray mass spectrum of a DMF solution containing sample 6. S20

21 Figure S18. Negative ion mode electrospray mass spectrum of a DMF solution containing sample 7. S21

22 Figure S19. Positive ion mode electrospray mass spectrum of a DMF solution containing sample 7. S22

23 Figure S20. Negative ion mode electrospray mass spectrum of a DMF solution containing sample 8. S23

24 Figure S21. Positive ion mode electrospray mass spectrum of a DMF solution containing sample 8. S24