S1

Supporting Information

Synthesis of metallophophaalkenes by reaction of organometallic

nucleophiles with a phosphaethynolato-borane

Daniel W. N. Wilson and Jose M. Goicoechea*

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road,

Oxford, OX1 3TA, U.K.

E-mail: jose.goicoechea@chem.ox.ac.uk

Contents

1. Experimental section

2. Single crystal X-ray diffraction data

3. References

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

S2

1. Experimental section

1.1. General synthetic methods

All reactions and product manipulations were carried out under an inert atmosphere of argon

or dinitrogen using standard Schlenk-line or glovebox techniques (MBraun UNIlab glovebox

maintained at <0.1 ppm H2O and <0.1 ppm O2). [B]OCP and NaFp* were synthesized

according to previously reported synthetic procedures.1,2 Chlorotrimethylsilane and

chloro(triphenylphosphine)gold(I) were purchased from Sigma Aldrich and used as received.

Hexane (hex; Sigma Aldrich HPLC grade), and toluene (tol; Sigma Aldrich HPLC grade)

were purified using an MBraun SPS-800 solvent system. C6D6 (Aldrich, 99.5%), was

degassed prior to use. All dry solvents were stored under argon in gas-tight ampoules.

Additionally chlorotrimethylsilane, C6D6, hexane, and toluene were stored over activated 3 Å

molecular sieves.

Additional characterization techniques: NMR spectra were acquired on a Bruker AVIII

500 MHz NMR spectrometer (1H 500 MHz, 13C 126 MHz) and Bruker AVIII 400 MHz NMR

spectrometer (31P 162 MHz, 11B 128 MHz). 1H and 13C NMR spectra were referenced to the

most downfield solvent resonance (1H NMR C6D6: δ = 7.16 ppm; 13C NMR C6D6: δ = 188.06

ppm). 31P{1H} and 11B{1H} spectra were externally referenced to an 85% solution of H3PO4

in H2O, and BF3·Et2O in C6D6, respectively. Elemental analyses were carried out by

Elemental Microanalyses Ltd. (Devon, U.K.). Samples (approx. 5 mg) were submitted in

sealed Pyrex ampoules.

S3

1.2. Compound syntheses

1.2.1. Synthesis of {[B](NaO)C=PFp*}2 {Na[1]}2

[B]OCP (150 mg, 0.34 mmol) was added to a suspension of NaFp* (92 mg, 0.34 mmol) in

toluene (2 mL). The solution darkened from light to dark orange. The solution was filtered to

remove any excess NaFp*, concentrated to approximately 50% of the original volume and

cooled overnight to yield {Na[1]}2 as red crystals (195 mg, 80.6%) suitable for single crystal

X-ray diffraction.

CHN Anal. Calcd. for C39H51BFeN2NaO3P: C, 65.38%; H, 7.18%; N, 3.91%. Found: C,

66.25%; H, 7.63%; N, 4.17%.

1H NMR (500 MHz, C6D6): δ (ppm) 7.31 (br s, 6H; ArH), 6.22 (s, 2H; (NCH)2), 3.72 (br s,

4H; {CH(CH3)2}), 1.56 (br s, 26H; Cp* CH3 and {CH(CH3)2}), 1.31 (d, 3JH–H = 7 Hz, 12H;

{CH(CH3)2}).

13C{1H} NMR (126 MHz, C6D6): δ (ppm) 222.05 (s, br; CO), 146.58 (ArC), 140.82 (ArC),

126.63 (ArC), 123.27 (ArC), 118.44 ((NCH)2), 94.93 (Cp*C), 28.20 (CH(CH3)2), 25.85

(Cp*CH3), 23.52 (CH(CH3)2), 9.32 (CH(CH3)2), 9.27 (CH(CH3)2). Note: [B]C(O)PFp* not

found, a small resonance at 145.79 ppm could be one half of the doublet with the other half

obscured by the peak at 146.58 ppm.

11B{1H} NMR (128 MHz, C6D6): δ (ppm) 25.5 (s).

31P{1H} NMR (162 MHz, C6D6): δ (ppm) 188.6 (s).

IR: ν = 1899.7 cm−1 (νasym, C≡O), 1942.6 cm−1 (νsym, C≡O).

S4

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

12.1

9

26.0

8

2.05

2.00

5.66

A (s)7.31

B (s)6.22

C (s)3.72

D (s)1.56

E (d)1.31

12.1

9

26.0

8

1.83

2.00

5.66

1.31

1.32

1.55

1.56

3.72

6.22

7.31

Figure S1: Room temperature 1H NMR of Na[1] in C6D6.

0102030405060708090100110120130140150160170180190200210220f1 (ppm)

9.27

9.32

23.5

225

.85

28.2

0

94.9

3

118.

4412

3.27

126.

63

140.

82

146.

58

222.

05

144.0144.5145.0145.5146.0146.5147.0147.5f1 (ppm)

145.

79

146.

58

Figure S2: Room temperature 13C{1H} NMR of Na[1] in C6D6.

S5

-10-5051015202530354045505560f1 (ppm)

25.5

2

Figure S3: Room temperature 11B{1H} NMR of Na[1] in C6D6.

-500-450-400-350-300-250-200-150-100-50050100150200250300350400450500f1 (ppm)

A (s)188.57

1.00

188.

57

Figure S4: Room temperature 31P{1H} NMR of Na[1] in C6D6.

S6

Figure S5: IR spectra of Na[1] in Nujol mull.

S7

1.2.2. Synthesis of [B](Me3SiO)C=PFp* (2)

To a solution of Na[1] (100 mg, 0.14 mmol) in toluene (2 mL) was added trimethylsilyl

chloride (18.3 mg, 0.17 mmol; 1.2 equivalents). A precipitate immediately formed and both

the 1H and 31P NMR spectra revealed quantitative conversion to [B](Me3SiO)C=PFp*. The

solution was filtered and the solvent removed under reduced pressure, yielding an orange

powder (91 mg, 85.0%). Recrystallisation from hexane yielded red crystals of

[B](Me3SiO)C=PFp* (2) suitable for X-ray diffraction.

CHN Anal. Calcd. for C42H60BFeN2O3PSi: C, 65.80%; H, 7.89%; N, 3.65%. Found: C,

65.35%; H, 7.61%; N, 3.99%.

1H NMR (500 MHz, C6D6): δ(ppm) 7.27–7.20 (m, 6H; ArH), 6.38 (s, 2H; (NCH)2), 3.69

(sept, 3JH–H = 7 Hz, 4H; {CH(CH3)2}), 1.45 (d, 3JH–H = 7 Hz, 12H; {CH(CH3)2}), 1.40 (s, 15H;

Cp* CH3), 1.25 (d, 3JH–H = 7 Hz, 12H; {CH(CH3)2}), 0.15 (s, 9H; SiMe3).

13C{1H} NMR (126 MHz, C6D6): δ (ppm) 217.04 (s, br; CO), 146.19 (d, 1JC–P = 33 Hz;

[B]C(O)PFp*), 145.92 (ArC), 140.72 (ArC), 127.03 (ArC), 124.00 (ArC), 120.14 ((NCH)2),

95.92(Cp*C), 28.67 (CH(CH3)2), 26.36 (CH(CH3)2), 23.34 (Cp*CH3), 9.33 (CH(CH3)2), 1.15

(SiCH3).

11B{1H} NMR (128 MHz, C6D6): δ(ppm) 23.3 (s, br).

31P{1H} NMR (162 MHz, C6D6): δ(ppm) 350.6 (s).

IR: ν = 1946.7 cm−1 (νasym, C≡O), 1993.7 cm−1 (νsym, C≡O).

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-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

A (s)6.38

B (m)7.22

C (hept)3.69

E (d)1.45

F (s)1.40

G (d)1.25

H (s)0.15

9.16

12.7

915

.56

12.6

3

4.00

1.92

6.84

0.15

1.24

1.25

1.40

1.44

1.46

1.61

3.65

3.66

3.67

3.69

3.70

3.71

3.73

6.38

7.21

7.21

7.22

7.24

7.25

7.26

7.27

Figure S6: Room temperature 1H NMR spectrum of 2 in C6D6.

-20-100102030405060708090100110120130140150160170180190200210220f1 (ppm)

1.15

9.33

23.3

426

.36

28.6

7

95.9

2

120.

1412

4.00

127.

03

140.

7214

5.92

146.

0614

6.33

217.

04

145.7145.9146.1146.3146.5f1 (ppm)

A (d)146.19

1.00

145.

92

146.

06

146.

33

Figure S7: Room temperature 13C{1H} NMR spectrum of 2 in C6D6.

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-90-80-70-60-50-40-30-20-100102030405060708090100110120130140f1 (ppm)

23.2

9

Figure S8: Room temperature 11B{1H} NMR spectrum of 2 in C6D6.

-500-450-400-350-300-250-200-150-100-50050100150200250300350400450500f1 (ppm)

A (s)350.64

1.00

350.

64

Figure S9: Room temperature 31P{1H} NMR spectrum of 2 in C6D6.

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Figure S10: IR spectra of 2 in Nujol mull.

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1.2.3. Synthesis of (PPh3)AuP{C(O)[B]}Fp* (3)

To a solution of Na[1] (100 mg, 0.14 mmol) in toluene (2 mL) was added

chloro(triphenylphosphene)gold(I) (69 mg, 0.14 mmol). The suspension was sonicated for 30

minutes, after which the NMR spectra showed complete consumption of the starting material.

The solution was filtered, and the solvent removed under reduced pressure. The resulting

orange oil was washing with hexane and recrystallised from toluene yielding analytically pure

orange crystals suitable for X-ray diffraction (87 mg, 60.1%).

CHN Anal. Calcd. for C57H66AuBFeN2O3P2: C, 59.39%; H, 5.77%; N, 2.43%. Found: C,

58.91%, H5.34 %; N 2.40 %.

1H NMR (500 MHz, C6D6): δ(ppm) 7.65–7.56 (m, 6H; ArH), 7.28–7.18 (m, 6H; ArH), 7.11–

6.99 (m, 9H; ArH), 6.26 (s, 2H; (NCH)2), 3.57 (sept, 3JH–H = 7 Hz, 4H; CH(CH3)2), 1.47 (s,

15H; Cp* CH3), 1.39 (d, 3JH–H = 7 Hz, 12H, CH(CH3)2), 1.19 (d, 3JH–H = 7 Hz, 12H,

CH(CH3)2).

13C{1H} NMR (126 MHz, C6D6): δ(ppm) 218.85 (s, br; CO), 146.38 (ArC), 140.68 (ArC),

138.40 (d, 1JC–P = 127.9 Hz; [B]C(O)PFp*), 134.75 (d, 2JC–P= 14 Hz; P(Ph)3 ArC), 131.80 (d,

1JC–P= 46 Hz; P(Ph)3 ArC), 131.21 (ArC), 129.23 (d, 3JC–P= 11 Hz; P(Ph)3 ArC), 127.21(ArC),

123.38 (ArC), 119.55 ((NCH)2), 94.65 (Cp*C), 30.23 (unknown impurity), 28.98 (CH(CH3)2),

26.00 (CH(CH3)2), 24.32 (Cp*CH3), 9.71(CH(CH3)2).

11B{1H} NMR (128 MHz, C6D6): δ(ppm) 21.8.

31P{1H} NMR (162 MHz, C6D6): δ(ppm) 98.8 (d, 2JP–P = 102 Hz), 43.3 (d, 2JP–P = 102 Hz).

IR: ν = 1954.8 cm−1 (νasym, C≡O), 2003.2 cm−1 (νsym, C≡O).

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1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

A (m)7.61

B (m)7.22

C (m)7.06

D (s)6.26

E (hept)3.57

F (s)1.47

G (d)1.39

H (d)1.19

11.7

3

12.2

114

.67

4.00

1.85

11.7

0

6.14

5.61

1.18

1.19

1.39

1.40

1.47

3.53

3.55

3.56

3.57

3.59

3.60

3.62

6.26

7.01

7.03

7.04

7.06

7.06

7.07

7.08

7.09

7.20

7.21

7.22

C6D

67.

247.

257.

267.

587.

597.

607.

617.

617.

627.

63

Figure S11: Room temperature 1H NMR spectrum of 3 in C6D6.

-20-100102030405060708090100110120130140150160170180190200210220f1 (ppm)

9.71

24.3

226

.00

28.9

830

.23

94.6

5

119.

5512

3.38

127.

2112

9.19

129.

2713

1.19

131.

2113

1.62

131.

9813

4.69

134.

8113

7.90

138.

9114

0.68

146.

38

218.

85

137.5138.0138.5139.0f1 (ppm)

A (m)138.40

1.00

137.

90

138.

91

Figure S12: Room temperature 13C{1H} NMR spectrum of 3 in C6D6.

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-70-60-50-40-30-20-100102030405060708090100f1 (ppm)

21.7

6

Figure S13: Room temperature 11B{1H} NMR spectrum of 3 in C6D6.

-500-450-400-350-300-250-200-150-100-50050100150200250300350400450500f1 (ppm)

A (d)98.75

B (d)43.26

0.65

1.00

42.9

443

.58

98.4

499

.07

42.543.043.598.098.599.099.5f1 (ppm)

42.9

4

43.5

8

98.4

4

99.0

7

Figure S14: Room temperature 31P{1H} NMR spectrum of 3 in C6D6.

S14

Figure S15: IR spectra of 3 in Nujol mull.

Figure S16: Enhanced view of carbonyl region of Figure S15.

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2. Single Crystal X-ray diffraction Data

Single-crystal X-ray diffraction data were collected using either an Oxford Diffraction

Supernova dual-source diffractometer equipped with a 135 mm Atlas CCD area detector.

Crystals were selected under Paratone-N oil, mounted on micromount loops and quench-

cooled using an Oxford Cryosystems open flow N2 cooling device. Data were collected at 150

K using mirror monochromated Cu Kα radiation (λ = 1.5418 Å; Oxford Diffraction

Supernova) and processed using the CrysAlisPro package, including unit cell parameter

refinement and inter-frame scaling (which was carried out using SCALE3 ABSPACK within

CrysAlisPro).3 Equivalent reflections were merged and diffraction patterns processed with the

CrysAlisPro suite. Structures were subsequently solved using direct methods and refined on

F2 using the SHELXL package.4

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Table S1. Selected X-ray data collection and refinement parameters for (Na[1])2, 2·0.25hex, and 3.

(Na[1])2 2 3Formula C87H123B2Fe2N4Na2O6P2 C43.5H63.5BFeN2O3PSi C57H66AuBFeN2O3P2

CCDC 1911021 1911022 1911023Fw [g mol–1] 1562.13 788.18 1152.68Crystal system triclinic triclinic triclinicSpace group P–1 P–1 P–1a (Å) 12.4481(4) 12.6726(7) 12.5793(6)b (Å) 16.8150(7) 14.4208(6) 12.6322(5)c (Å) 22.2412(11) 25.6379(10) 17.8449(6)α (°) 96.817(4) 78.827(4) 86.392(3)β (°) 94.522(3) 86.973(4) 73.088(4)γ (°) 107.257(4) 78.977(4) 81.048(4)V (Å3) 4382.4(3) 4511.1(4) 2679.5(2)Z 2 4 2Radiation, λ (Å) Mo Kα, 0.71073 Cu Kα, 1.54184 Cu Kα, 1.54184Temp (K) 150(2) 150(2) 150(2)ρcalc (g cm–3) 1.184 1.161 1.429μ (mm–1) 0.429 3.556 8.145Reflections collected 35282 39615 28840Independent reflections 15427 18631 11081Parameters 975 963 617R(int) 0.0424 0.0476 0.0453R1/wR2,[a] I ≥ 2σI (%) 5.05/10.25 5.38/13.81 3.96/9.55R1/wR2,[a] all data (%) 8.12/11.31 7.17/15.56 4.83/9.93GOF 1.042 1.039 1.029R1 = [Σ||Fo| – |Fc||]/Σ|Fo|; wR2 = {[Σw[(Fo)2 – (Fc)2]2]/[Σw(Fo

2)2}1/2; w = [σ2(Fo)2 + (AP)2 + BP]–1, where P = [(Fo)2 + 2(Fc)2]/3 and the A and B values are

0.0412 and 0.36 for (Na[1])2, 0.0725 and 1.76 for 2, and 0.0493 and 4.07 for 3.

S17

3. References

1 D. W. N. Wilson, A. Hinz and J. M. Goicoechea, Angew. Chem. Int. Ed. 2018, 57,

2188–2193.

2 J. R. Green. Sodium Dicarbonylcyclopentadienylferrate in Encycl. Reagents Org.

Synth., John Wiley & Sons, Ltd, Chichester, UK, 2001.

3 CrysAlisPro, Agilent Technologies, Version 1.171.35.8.

4 (a) G. M. Sheldrick in SHELXL97, Programs for Crystal Structure Analysis (Release

97-2), Institut für Anorganische Chemie der Universität, Tammanstrasse 4, D-3400

Göttingen, Germany, 1998; (b) G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46,

467−473; (c) G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112−122.