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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2018 Electronic Supporting Information robing steric influences on electrophilic phosphonium cations: A comparison of [(3,5-( ) 2 C 6 H 3 ) 3 ] + and [(C 6 5 ) 3 ] + James H. W. Laortune, Kevin M. Szkop, arah E. arinha, Timothy C. Johnstone, Shawn ostle, and Douglas W. Stephan * 1

2 This D file includes: 1. Synthesis (3,5-( ) 2 C 6 H 3 ) 3 2 (1) [(3,5-( ) 2 C 6 H 3 ) 3 ][B(C 6 5 ) 4 ] (2) Air Stability Test Gutmann-Beckett Method Silane Stability Test Lewis Acid Catalysis Dimerization of 1,1-diphenylethylene Hydroarylation of diphenylamine with 1,1 -diphenylethylene Double hydroarylation of di-para-tolylamine with para-tolylacetylene hosphorane/hosphonium Exchange Experiments Competition between 2 and (C 6 5 ) Competition between 1 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] hosphorane/hosphonium Self-Exchange Experiments Self-Exchange of (C 6 5 ) 3 2 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] Self-Exchange of 1 and Computational Details References

3 1. Synthesis 2.1 (3,5-( ) 2 C 6 H 3 ) 3 2 (1) igure S1. 1 H (CDCl 3 ) NMR spectrum of 1. 3

4 igure S2. 19 { 1 H} (CDCl 3 ) NMR spectrum of igure S3. 31 { 1 H} (CDCl 3 ) NMR spectrum of igure S4. 13 C{ 1 H} (CDCl 3 ) NMR spectrum of 1. 4

5 igure S5. 13 C{ 1 H} (CDCl 3 ) NMR spectrum of 1, expanded region. 2.2 [(3,5-( ) 2 C 6 H 3 ) 3 ][B(C 6 5 ) 4 ] (2) [B(C 6 5 ) 4 ] igure S6. 1 H (CD 2 Cl 2 ) NMR spectrum of 2. 5

6 igure S7. 11 B{ 1 H} (CD 2 Cl 2 ) NMR spectrum of igure S8. 19 { 1 H} (CD 2 Cl 2 ) NMR spectrum of igure S9. 31 { 1 H} (CD 2 Cl 2 ) NMR spectrum of 2. 6

7 igure S C{ 1 H} (CD 2 Cl 2 ) NMR of igure S C{ 1 H} (CD 2 Cl 2 ) NMR of 2, expanded region. 7

8 2. Air Stability Test 0 min 5 min igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of 2 after exposure to air. 0 min 5 min igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of 2 after exposure to air, expanded region. 8

9 3. Gutmann-Beckett Method LA O O LA Et Et Et Et Et Et Et Et Et [B(C 6 5 ) 4 ] Et 3 O Et Et O igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of Gutmann-Beckett method with Silane Stability Test Et 3 Si igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of 2 after exposure to Et 3 SiH for 16 hours. 9

10 5. Lewis Acid Catalysis 5.1 Dimerization of 1,1-diphenylethylene 2 eq 1 mol% <cat> CH 2 Cl 2, rt, 30 min h h h 2 = 78% [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] = 86% [1] igure S16. 1 H (CDCl 3 ) NMR spectrum from the catalytic dimerization of 1,1- diphenylethylene by

11 5.2 Hydroarylation of diphenylamine with 1,1 -diphenylethylene H N 1.5 mol% <cat> CH 2 Cl 2, rt, 6 h H N h h 2 = 84% [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] = >99% [2] MS (EI ionization), [m/z]: (M-H) igure S H (CDCl 3 ) NMR spectrum from the catalytic hydroarylation of diphenylamine with 1,1 -diphenylethylene by

12 5.3 Double hydroarylation of di-para-tolylamine with para-tolylacetylene H N 5 mol % <cat> CH 2 Cl 2, rt, 24 h H N MS (EI ionization), [m/z]: (M-H). 2 = 91% [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] = 74% igure S18. 1 H NMR spectrum for the catalytic double hydroarylation of di-para-tolylamine with para-tolylacetylene by 2. 12

13 6. hosphorane/hosphonium Exchange Experiments 5.1 Competition between 2 and (C 6 5 ) 3 2 [B(C 6 5 ) 4 ] C 6 5 C 6 5 C 6 5 DCM, rt 24 h C 6 C C 6 5 [B(C 6 5 ) 4 ] igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of 2 and (C 6 5 )

14 5.1 Competition between 1 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] C 6 C C 6 5 [B(C 6 5 ) 4 ] DCM, rt 24 h [B(C 6 5 ) 4 ] C 6 5 C 6 5 C igure S { 1 H} (CH 2 Cl 2 ) NMR spectrum of 1 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ]. 14

15 7. hosphorane/hosphonium Self-Exchange Experiments [AA] [AB] = Eq n 1 ( 1 2k 2 )(1 e 2kτ ) 2k 2 + (1 2k 2 )(e 2kτ ) 2τ = 1 k ln (1 + ( [AB] [AA]) ) Eq n Self-Exchange of (C 6 5 ) 3 2 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] C 6 5 C 6 5 C 6 5 C 6 C C 6 5 [B(C 6 5 ) 4 ] DCM, rt C 6 C C 6 5 [B(C 6 5 ) 4 ] C 6 5 C 6 5 C

16 igure S21. 2D NOSY/EXSY of (C 6 5 ) 3 2 and [(C 6 5 ) 3 ][B(C 6 5 ) 4 ]. 16

17 = 400 ms = 300 ms = 250 ms = 200 ms = 100 ms = 50 ms igure S Selective 1D 19 NMR exchange spectroscopy (SEXY) for phosphorus-substituted meta-c- [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] exchanging with (C 6 5 )

18 2(τ) igure S ln(1+[ab]/[aa]) Graph of 2τ vs ln (1+([AB]/[AA])) for phosphorus-substituted meta-c- of [(C 6 5 ) 3 ][B(C 6 5 ) 4 ] exchanging with (C 6 5 ) 3 2. k = s

19 6.2 Self-Exchange of 1 and 2 [B(C 6 5 ) 4 ] DCM, rt [B(C 6 5 ) 4 ] = 400 ms = 300 ms = 250 ms = 200 ms = 100 ms = 50 ms igure S Selective 1D 19 NMR exchange spectroscopy (SEXY) for of 2 exchanging with 1. 19

20 2(τ) ln(1+[ab]/[aa]) igure S25. Graph of 2τ vs ln (1+([AB]/[AA])) for of 2 exchanging with 1. k =

21 8. Computational Details Table S1. Cartesian coordinates (Å) of [(3,5-( ) 2 C 6 H 3 ) 3 ] + Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

22 Table S2. Cartesian coordinates (Å) of (3,5( ) 2 C 6 H 3 ) 3 2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

23 Table S3. Cartesian coordinates (Å) of [(C 6 5 ) 3 ] + Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

24 Table S4. Cartesian coordinates (Å) of (C 6 5 ) 3 2 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

25 Table S5. Cartesian coordinates (Å) of B(C 6 5 ) 3 Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

26 Table S6. Cartesian coordinates (Å) of [B(C 6 5 ) 3 ] - Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z Table S7. Cartesian coordinates (Å) of C 2 O Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

27 Table S8. Cartesian coordinates (Å) of [ O] - Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z References [1] M. érez, L. J. Hounjet, C. B. Caputo, R. Dobrovetsky, D. W. Stephan, J. Am. Chem. Soc., 2013, 135, [2] M. erez, T. Mahdi, L. J. Hounjet, D. W. Stephan, Chem. Commun., 2015, 51,